CN115305534A - High-speed electro-coppering additive for advanced packaging and preparation method thereof - Google Patents
High-speed electro-coppering additive for advanced packaging and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-speed electro-coppering additive for advanced packaging and a preparation method thereof, wherein the high-speed electro-coppering additive comprises the following components: 80-120g/L of blue vitriol; 180-220g/L of sulfuric acid; 40-80g/L of chloride ions; leveling agent 50-200mg/L; 10-40mg/L of brightener; 100-1000mg/L inhibitor; 6-10mg/L of electroplating cylinder opening agent. The invention mainly evaluates the copper plating performance of the acid copper plating brightener system from the aspects of deep plating capability of the through blind hole, ductility of the electroplated copper foil, thermal stress performance of the plating layer, morphology of the plating layer and the like, thereby detecting whether the brightener can be primarily applied to copper plating of a printed circuit board.
Description
Technical Field
The invention relates to the technical field of electroplating deposition, in particular to a high-speed electro-coppering additive for advanced packaging and a preparation method thereof.
Background
In recent years, with the rapid development of the electronic information industry, printed circuit boards are an indispensable important support, small as intelligent chips and microcomputers, and large as computers, communication electronic equipment, military weapon systems and aerospace circuit boards, and as long as electronic components such as integrated circuits are printed circuit boards. Metallized through holes or blind holes are used in the multilayer circuit board to realize conduction among different layers, so that signals are interconnected. The through hole copper electroplating is an important way for realizing through hole metallization, and is also a very important technology in the manufacturing process of the multilayer PCB. With the increasing complexity of electronic equipment and the increasing number of required parts, the printed circuit board lines and parts are also more and more intensive, and a large number of high-density interconnection multi-level blind hole board technologies make a great deal of breakthrough.
The printed circuit board can be divided into a rigid board, a flexible board and a rigid-flex combination board according to the hardness of the finished product. The structural boards are further divided into single-sided boards, double-sided boards and conventional multilayer boards, and flexible boards and high-density interconnection multilayer boards have promising development prospects. The rigid board is a printed board made of rigid base materials which are not easy to bend and have certain toughness, and can provide a certain supporting effect for electronic elements attached to the rigid board. The flexible board is a printed board made of a flexible base material, and is also called a flexible board. It is characterized by being bendable. Different boards can be divided into single-sided boards, double-sided boards and multilayer boards according to the structure, wherein more than two layers of conductive patterns are alternately adhered with insulating materials, and the conductive patterns among the layers are interconnected. The PCB is formed by a plurality of layers of double-sided boards, wherein an insulating layer is arranged between each layer of double-sided boards and then firmly adhered (pressed), most of the PCB at present are generally multi-layer boards, the aspect ratio of the PCB is higher and higher, the aspect ratio and the ratio of the board thickness to the aperture are higher and higher, and the requirement on electroplating liquid medicine is higher and higher due to the fact that the board thickness needs to be very good in hole filling permeability of the electroplating liquid medicine.
Due to the excellent electrical conductivity, thermal conductivity and reliability of copper, the copper interconnection technology has the advantages of high current carrying capacity, cost saving and the like, and is widely applied to BEOL (back electro-optical) manufacturing and advanced packaging processes of semiconductors. In the advanced packaging process, copper interconnection is the key process, and the process is divided into RDL pattern transfer electroplating and bump electroplating according to the form of electroplated copper. Compared with the traditional lead bonding, the packaging cost can be reduced by 20 percent by adopting the advanced packaging process of electro-coppering interconnection, the advanced packaging technology is rapidly developed in recent years, and the application range is gradually expanded.
Copper electroplating is the most prominent method for achieving electrical interconnections in electronic products, and organic additives are commonly used to achieve uniform conductive patterns and to obtain coatings with good properties. The copper plating additive mainly comprises a brightening agent, an inhibitor and a leveling agent. The plating solution mainly consists of copper sulfate and sulfuric acid, which both participate in the electrode process. They are interdependent in the bath. As the concentration of sulfuric acid in the solution increases, the solubility of copper sulfate decreases, but the conductivity of the solution increases significantly. The copper sulfate concentration in the plating solution is too low, and the plating layer in a high current area is easy to be burnt; the copper sulfate concentration is too high, and the dispersing ability and leveling ability of the plating solution are lowered.
For example, chinese patent CN112030199B discloses a high speed electro-coppering additive and electroplating solution for advanced packaging, which comprises copper salt, acid, 20-80ppm of chloride ion, 2-2000ppm of accelerator, 5-5000ppm of carrier, 3-3000ppm of leveling agent; the content of copper ions in the copper salt is 20-90g/L, and the content of acid is 0.5-5.0mol/L; the accelerator is a dithiocarbamate derivative, the carrier is an EO-PO block copolymer, and the leveler composition is a composition that includes a source of copper ions and at least one leveler. The invention can effectively solve the technical problems of pockmarks, roughness, cavities, poor uniformity, poor Bump appearance, inconsistent heights of different positions and the like which are easy to appear in advanced packaging Bump/RDL electroplating
However, in the preparation process of the additive for the high-speed copper plating solution, besides the effect achieved by the additive tape, the consumption rate of the additive is also considered, the consumption rate of the additive is too high, so that the time of the copper plating solution is shortened, the use efficiency of the copper plating solution is reduced, the concentration content of each additive is also a requirement, and specific data are matched with the selected additive, for example, the concentration of copper sulfate in the copper plating solution is too low, and a plating layer in a high-current area is easy to scorch; the copper sulfate concentration is too high, resulting in a decrease in the dispersing ability and leveling ability of the copper plating solution.
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
The present invention is directed to a high-speed electro-coppering additive for advanced packaging and a method for preparing the same, which overcome the above-mentioned problems of the prior art.
Therefore, the invention adopts the following specific technical scheme:
a high speed electro-coppering additive for advanced packaging, the solution consisting of:
80-120g/L of blue vitriol;
180-220g/L of sulfuric acid;
40-80g/L of chloride ions;
leveling agent 50-200mg/L;
10-40mg/L of brightener;
100-1000mg/L inhibitor;
6-10mg/L of electroplating cylinder opening agent.
Further, the leveling agent includes a polyalkoxy compound, a polythioalkyl compound, or an alkoxy compound of different alkyl substituents.
Further, the brightening agent is sodium polydithio dipropyl sulfonate.
Further, the inhibitor includes polyethylene glycol, an oxyethylene or oxypropylene copolymer.
Further, the electroplating cylinder opening agent comprises the following components in parts by weight of 1:1, and a manganese-containing compound.
Further, the aldehyde compound is a-diketone compound.
Further, the manganese-containing compound is manganese naphthenate.
According to another aspect of the present invention, there is also provided a method for preparing a high-speed electrolytic copper plating additive for advanced packaging, the preparation process comprising the steps of:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3, sequentially adding sodium polydithio-dipropyl sulfonate, polyethylene glycol and a leveling agent into the base liquid, and stirring;
s4, adding an electroplating cylinder opening agent into the base liquid in the stirring process;
and S5, uniformly stirring to obtain the high-speed electro-coppering additive.
Further, the indoor temperature of the instrument is controlled to be 23 to 26 ℃.
Further, the scanning potential range is-0.225 to 1.625V.
Chloride ion: the chloride ion is also an additive in the electroplating bath solution, and is an anode activator and a plating layer stress relieving agent. The chloride ions can help the anode to dissolve, and the chloride ions and the additive act synergistically to enable the coating to be bright and smooth, and can also reduce the tensile stress of the coating.
Inhibitor (B): the carrier is also called as a non-ionic surfactant or an anionic surfactant, is used as a carrier of a brightener and a leveling agent, improves the solubility and the activity on an electrode of the brightener and the leveling agent, has the functions of coating uniformity and grain refinement, is also called as a carrier, is mainly used for assisting the brightener to be uniformly distributed to a plating surface, can improve the polarization overpotential of the electrode, inhibits the deposition of copper, reduces the surface tension of bath solution, increases the wetting effect, is often called as a wetting agent, assists the brightener to be distributed on the surface of a plating part, enables the copper surface to have glossiness, can play a role under the assistance of chloride ions, is not stable, can be decomposed into the carrier with lower molecular weight in the bath solution, forms a diffusion layer with uniform thickness with an original non-uniform water film, enables the secondary distribution of current to be more uniform, has certain leveling capability, is high in molecular weight, is high in electropositivity, is easy to be adsorbed on the plating part of a cathode, is easily adsorbed on the plating part of the cathode due to the carrier, has low diffusion system, generates a lower limit current density ratio, and has the effect of inhibiting the secondary deposition of a side effect of copper, and reduces the occurrence of a side effect of copper deposition easily.
Brightening agent: under the assistance of chloride ions, depolarization can be generated, overpotential is reduced, copper plating speed is accelerated, the brightener is also called an accelerator, the brightener also enters a plating layer to participate in a crystal structure, the natural crystallization mode of intervening copper atom deposition is influenced, and the brightener is also called a grain refiner, and certainly has a certain polarization increasing effect because the surface of the plating layer becomes smooth and light-reflecting, so the brightener is called the brightener.
Leveling agent: the additive has strong electropositivity, is stronger than a carrier agent, is easy to be adsorbed at a position with larger surface current density of a plated part, competes with copper ions, enables the copper ions to be difficult to deposit at a high current position, but does not influence the deposition of the copper ions at a low current region, enables an originally uneven surface to become flat, and is called a leveling agent, the leveling capability of the leveling agent is closely related to the structure of a substituent group, conjugated one CH = CH-CH = CH-bond exists in a molecule, so that the adsorption at a cathode is greatly enhanced, the reduction of the copper ions at the cathode is effectively inhibited, the molecule with an azo group has the leveling capability due to the existence of a conjugated structure, and the electron originally limited between two atoms is changed from a localized region to a delocalized region due to the characteristic of the conjugated structure, so that the electron is shared by more than two atoms, the excitation energy of the molecule is reduced, the energy of transition from a non-bonded orbit or pi-bonded orbit to a reverse-bonded orbit is reduced, the leveling capability is influenced by the formation of the conjugated bond, the leveling capability, the induced effect, the hyperconjugated effect and the leveling capability of the leveling effect is also influenced by the same effect, the steric hindrance effect, the leveling effect is better, and the leveling effect is beneficial to the leveling effect on the one hand, the other hand, the leveling effect of the leveling effect, the leveling effect is increased.
Electroplating a cylinder opening agent: the consumption rate of the brightener and the leveling agent is slowed down, and the aldehyde compound added in the electroplating cylinder opening agent has certain effect of accelerating the deposition of the plating layer at the bottom of the copper plating layer at the corner of the bottom of the blind hole plate.
The invention has the beneficial effects that:
1. the invention mainly evaluates the copper plating performance of the acid copper plating gloss agent system from the aspects of deep plating capability of the through blind hole, ductility of the electroplated copper foil, thermal stress performance of a plating layer, morphology of the plating layer and the like, thereby detecting whether the gloss agent can be primarily applied to copper plating of a printed circuit board.
2. The invention solves the problem that the plating layer in the hole is thinner under the high current density of the cathode by the high-speed coppering agent, so that the plating layer has higher deep plating capability and the efficiency of a production line is improved.
3. When the method is used specifically, a Harlin groove is used for carrying out a small test experiment, the appearance condition of a VCP line high current density board surface is simulated, all components of a polishing agent are selected according to the appearance condition of the board surface for screening, a full factor experiment is designed, the influence of all components of the polishing agent on the deep plating capacity of a through hole under different concentrations is researched, the concentration parameter of all components of the polishing agent is optimized, a simulation amplification experiment is carried out in a self-made 40L simulation VCP groove, a through blind hole board is tested, the deep plating capacity, ductility, crystal morphology, thermal shock and other plating layer reliability of a copper plating layer under different current densities are researched, the influence factors influencing the performance of each plating layer are researched, a cyclic voltammetry stripping method is used for establishing an analysis method of all components of the polishing agent, the accuracy of an analysis result of the analysis method is tested, the stability of an acidic copper plating agent is researched from the mechanism, the consumption of the polishing agent under different current densities is tested, measures are adopted for improving the stability of all components of the polishing agent in a groove liquid to keep the components balanced and stable, and the quality of the plating layer is better guaranteed.
4. After the acid copper plating formulation is formed, the optical agent can be kept stable in the tank liquid, and a proper printed circuit board enterprise can be selected for VCP production line trial, so that the experiment is further amplified, and the comprehensive performance of the plating layer of the acid copper plating optical agent is tested and followed in time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a high speed electro-coppering additive for advanced packaging and method of making the same according to an embodiment of the present invention;
FIG. 2 is a graph of the copper plating solution ratios of Table 1 in a high speed electro-coppering additive for advanced packaging and method of making the same according to an embodiment of the present invention;
fig. 3 is a graph of the tensile strength ratios of table 1 in a flowchart of a high speed electro-coppering additive for advanced packaging and a method for preparing the same according to an embodiment of the present invention.
Detailed Description
For further explanation of the various embodiments, the drawings which form a part of the disclosure and which are incorporated in and constitute a part of this specification, illustrate embodiments and, together with the description, serve to explain the principles of operation of the embodiments, and to enable others of ordinary skill in the art to understand the various embodiments and advantages of the invention, and, by reference to these figures, reference is made to the accompanying drawings, which are not to scale and wherein like reference numerals generally refer to like elements.
According to an embodiment of the present invention, a high-speed electro-coppering additive for advanced packaging and a method for preparing the same are provided.
Example one
A high speed electrolytic copper plating additive for advanced packaging, the solution consisting of:
80g/L of blue vitriol;
180g/L of sulfuric acid;
40g/L of chloride ions;
leveling agent 50mg/L;
brightener 10mg/L;
100mg/L of inhibitor;
6mg/L of electroplating cylinder opener.
In one embodiment, the leveler is a polyalkoxy compound.
In one embodiment, the brightener is sodium polydithio dipropyl sulfonate.
In one embodiment, the inhibitor comprises polyethylene glycol.
In one embodiment, the electroplating cylinder opening agent is prepared from the following components in parts by weight of 1:1 and a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3', sequentially adding sodium polydithio-dipropyl sulfonate, polyethylene glycol and polyalkoxy compounds into the base liquid, and stirring;
s4, adding an electroplating cylinder opening agent into the base liquid in the stirring process;
and S5, uniformly stirring to obtain the high-speed electro-coppering additive.
In one embodiment, the temperature in the instrument chamber is controlled to be 25 ℃.
In one embodiment, the scanning potential ranges from-0.225 to 1.625V.
Example two
A high speed electro-coppering additive for advanced packaging, the solution consisting of:
100g/L of blue vitriol;
200g/L of sulfuric acid;
60g/L of chloride ions;
leveling agent 125mg/L;
25mg/L of brightener;
550mg/L of inhibitor;
electroplating cylinder opening agent is 8mg/L.
In one embodiment, the leveler is a polythioalkyl compound.
In one embodiment, the brightener is sodium polydithio dipropyl sulfonate.
In one embodiment, the inhibitor is an oxyethylene group.
In one embodiment, the electroplating cylinder opening agent is prepared from the following components in parts by weight of 1:1 with a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3', sequentially adding sodium polydithio-dipropyl sulfonate, polyethylene glycol and a polythioalkyl compound into the base liquid, and stirring;
s4, adding an electroplating cylinder opening agent into the base liquid in the stirring process;
and S5, uniformly stirring to obtain the high-speed electro-coppering additive.
In one embodiment, the temperature in the instrument chamber is controlled to be 25 ℃.
In one embodiment, the scanning potential ranges from-0.225 to 1.625V.
EXAMPLE III
A high speed electrolytic copper plating additive for advanced packaging, the solution consisting of:
120g/L of blue vitriol;
220g/L of sulfuric acid;
80g/L of chloride ions;
leveling agent 200mg/L;
40mg/L of brightener;
1000mg/L of inhibitor;
10mg/L of electroplating cylinder opener.
In one embodiment, the leveler is an alkoxide of different alkyl substituents.
In one embodiment, the brightener is sodium polydithio dipropyl sulfonate.
In one embodiment, the inhibitor is an oxypropylene copolymer.
In one embodiment, the electroplating cylinder opening agent is prepared from the following components in parts by weight of 1:1 with a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3' ' ', adding sodium polydithio dipropyl sulfonate, polyethylene glycol and alkoxy compounds with different alkyl substituents into the base liquid in sequence, and stirring;
s4, adding an electroplating cylinder opening agent into the base liquid in the stirring process;
and S5, uniformly stirring to obtain the high-speed electro-coppering additive.
In one embodiment, the instrument chamber temperature is controlled to 25 ℃.
In one embodiment, the scanning potential ranges from-0.225 to 1.625V.
Comparative example 1
A high speed electro-coppering additive for advanced packaging, the solution consisting of:
120g/L of blue vitriol;
220g/L sulfuric acid;
80g/L of chloride ions;
leveling agent 200mg/L;
40mg/L of brightener;
1000mg/L of inhibitor.
In one embodiment, the leveler is a polyalkoxy compound.
In one embodiment, the brightener is sodium polydithio dipropyl sulfonate.
In one embodiment, the inhibitor is polyethylene glycol.
In one embodiment, the electroplating cylinder opening agent is prepared from the following components in parts by weight of 1:1 with a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3' ' ', adding sodium polydithio dipropyl sulfonate, polyethylene glycol and polyalkoxy compound into the base liquid in sequence, and stirring;
and S4', uniformly stirring to obtain the high-speed electro-coppering additive.
In one embodiment, the temperature in the instrument chamber is controlled to be 25 ℃.
In one embodiment, the scanning potential range is-0.225 to 1.625V.
Comparative example No. two
A high speed electrolytic copper plating additive for advanced packaging, the solution consisting of:
120g/L of blue vitriol;
220g/L of sulfuric acid;
80g/L of chloride ions;
leveling agent 200mg/L;
inhibitor 1000mg/L.
In one embodiment, the leveler is a polyalkoxy compound.
In one embodiment, the brightener is sodium polydithio dipropyl sulfonate.
In one embodiment, the inhibitor is polyethylene glycol.
In one embodiment, the electroplating cylinder opening agent comprises the following components in parts by weight of 1:1, and a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3' ' ', adding sodium polydithio dipropyl sulfonate, polyethylene glycol and polyalkoxy compound into the base liquid in sequence, and stirring;
s4', and stirring uniformly to obtain the high-speed electro-coppering additive.
In one embodiment, the temperature in the instrument chamber is controlled to 25 ℃.
In one embodiment, the scanning potential range is-0.225 to 1.625V.
Comparative example No. three
A high speed electro-coppering additive for advanced packaging, the solution consisting of:
120g/L of blue vitriol;
220g/L of sulfuric acid;
80g/L of chloride ions;
leveling agent 200mg/L;
1000mg/L of inhibitor;
the accelerator is 10mg/L.
In one embodiment, the leveler is a polyalkoxy compound.
In one embodiment, the inhibitor is polyethylene glycol.
In one embodiment, the electroplating cylinder opening agent is prepared from the following components in parts by weight of 1:1 with a manganese-containing compound.
In one embodiment, the aldehyde compound is a-diketone compound.
In one embodiment, the manganese-containing compound is manganese naphthenate.
The preparation method comprises the following steps of selecting and preparing the raw material components according to the concentration ratio for preparing the chemical copper plating solution, and preparing the high-speed electro-coppering additive for advanced packaging, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3' ' ' ' ', adding polyethylene glycol into the base solution, and stirring;
s4' ' ', adding an accelerator into the base liquid in the stirring process;
and S5', uniformly stirring to obtain the high-speed electro-coppering additive.
In one embodiment, the temperature in the instrument chamber is controlled to be 25 ℃.
In one embodiment, the scanning potential range is-0.225 to 1.625V
Examples of the experiments
Preparing 1L of chemical copper plating solution according to the concentration of each component in seven groups according to the first, second and third embodiments and the first, second and third comparative examples, placing the PCB with the same specification and size in the copper plating solution for copper plating by using the corresponding copper plating process, removing the PCB after the copper plating is finished, performing quality and adhesion test (dividing the surface of the PCB into a plurality of grids with the size of 1 multiplied by 1mm by using a cutter, observing whether grids in the grids fall off or not), and recording experimental data in the copper plating process in real time, as shown in Table 1 (shown in figures 2-3) -Table 2:
table 1: comparison of plating Performance of electroless copper plating solutions
Temperature (. Degree.C.) | Elongation (%) | Tensile strength (Mpa) | Additive consumption Rate (%) | |
Example one | 25 | 35.2 | 268 | 5 |
Example two | 25 | 34.2 | 252 | 5 |
EXAMPLE III | 25 | 36.5 | 274 | 5 |
Comparative example 1 | 25 | 30.2 | 212 | 6 |
Comparative example No. two | 25 | 24.2 | 186 | 10 |
Comparative example No. three | 25 | 32.4 | 240 | 10 |
Table 2: content ratio of copper sulfate in copper plating solution
Copper sulfate content (g/L) | Current Density (A/dm) 2 ) | Quality of coating | |
Example one | 75 | 0.6 | Smooth, fine and bright plating layer |
Example two | 75 | 0.8 | Smooth, fine and bright plating layer |
EXAMPLE III | 100 | 0.6 | The plating layer is level, fine, smooth and bright |
Comparative example 1 | 100 | 0.8 | The plating layer is level, fine, smooth and bright |
Comparative example No. two | 50 | 0.6 | Is slightly rough |
Comparative example No. three | 50 | 0.8 | With rough lines |
As can be seen from the table 1, the electroless copper plating solution disclosed by the invention can form a fine, smooth and bright coating on the surface of a PCB, greatly improves the coating efficiency, has a good anti-stretching effect, has the characteristics of environmental protection, high efficiency and long service life of internal components, and is suitable for the fields of industrial processing, high-quality preparation of PCB and the like.
In conclusion, by means of the technical scheme, the invention mainly evaluates the copper plating performance of the acid copper plating agent system from the aspects of the deep plating capability of the through blind hole, the ductility of the electroplated copper foil, the thermal stress performance of the plating layer, the morphology of the plating layer and the like, so as to test whether the agent can be primarily applied to copper plating of the printed circuit board. The invention solves the problem that the plating layer in the hole is thinner under the high current density of the cathode by the high-speed copper plating brightener, so that the plating layer has higher deep plating capability and the efficiency of a production line is improved. The acid copper electroplating polishing agent enables the blind holes and the through hole plates to be subjected to common bath electroplating at the same time, and the problem of plating the blind holes of the crab legs can be solved by adding an additive, so that the electroplating process is simplified. When the device is used specifically, a small experiment is carried out by using a Harlin groove, the appearance condition of a VCP line high-current density board surface is simulated, all components of a light agent are selected according to the appearance condition of the board surface for screening, a full-factor experiment is designed, the influence of all light agent components on the deep plating capacity of the through hole under different concentrations is researched, the concentration parameters of all components of the light agent are optimized, a simulation amplification experiment is carried out in a self-made 40L simulation VCP groove, and the deep plating capacity, the ductility, the crystal morphology, the thermal shock and other reliable plating layer performances of a copper plating layer under different current densities are researched by using a test through blind hole board. And the influence factors influencing the performance of each coating are researched. And (3) establishing an analysis method for each component of the light agent by using a cyclic voltammetry stripping method and testing the accuracy of an analysis result of the analysis method. Most importantly, the stability of the acidic copper brightener was studied mechanistically. And the consumption of the light-emitting agent under different current densities is tested, and measures are taken to improve the stability of each component of the light-emitting agent in the bath solution so as to keep the light-emitting agent balanced and stable, thereby better ensuring the quality of a plating layer. After the acid copper plating formula is formed, the light-emitting agent can be kept stable in the tank liquid, and a proper printed circuit board enterprise can be selected for VCP production line trial. The experiment is further amplified, and the comprehensive performance of the plating layer of the acid electrolytic copper plating polishing agent is tested and followed up in time.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A high speed electro-coppering additive for advanced packaging, characterized in that the solution consists of:
80-120g/L of blue vitriol;
180-220g/L of sulfuric acid;
40-80g/L of chloride ions;
leveling agent 50-200mg/L;
10-40mg/L of brightener;
100-1000mg/L inhibitor;
6-10mg/L of electroplating cylinder opening agent.
2. The high speed electrolytic copper plating additive for advanced packaging as claimed in claim 1, wherein the leveler comprises a polyalkoxy compound, a polythioalkyl compound or an alkoxy compound of different alkyl substituents.
3. The high speed electrolytic copper plating additive for advanced packaging as claimed in claim 2, wherein the brightener is sodium polydithio dipropyl sulfonate.
4. The additive for high speed electrolytic copper plating for advanced packaging as claimed in claim 3, wherein the inhibitor comprises polyethylene glycol, ethylene oxide or propylene oxide copolymer.
5. The high-speed electrolytic copper plating additive for advanced packaging as claimed in claim 4, wherein the electrolytic copper plating opening agent comprises 1:1 and a manganese-containing compound.
6. The high-speed electrolytic copper plating additive for advanced packaging according to claim 5, wherein the aldehyde compound is a-diketone compound.
7. The high speed electrolytic copper plating additive for advanced packaging as claimed in claim 6, wherein the manganese containing compound is manganese naphthenate.
8. A method for preparing the high-speed electrolytic copper plating additive for advanced packaging, which is used for preparing the high-speed electrolytic copper plating additive for advanced packaging as claimed in claim 7, wherein the preparation process comprises the following steps:
s1, respectively weighing appropriate amount of copper sulfate pentahydrate, sulfuric acid and chloride ions, and mixing the copper sulfate pentahydrate, the sulfuric acid and the chloride ions according to the weight ratio of 5:10:3, mixing the mixture with water to obtain a base solution, and placing the base solution into a CVS analyzer;
s2, setting plating conditions: the stirring speed of the plating solution is 2600rpm/min, and the scanning speed is 100mV/s;
s3, sequentially adding sodium polydithio-dipropyl sulfonate, polyethylene glycol and a leveling agent into the base liquid, and stirring;
s4, adding an electroplating cylinder opening agent into the base liquid in the stirring process;
and S5, uniformly stirring to obtain the high-speed electro-coppering additive.
9. The method for preparing the high-speed electro-coppering additive for advanced packaging as claimed in claim 8, wherein the indoor temperature of the instrument is controlled to be 23-26 ℃.
10. The method for preparing the high-speed electro-coppering additive for advanced packaging as claimed in claim 8, wherein the scanning potential range is-0.225 to 1.625V.
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