CN111020649B

CN111020649B - Leveling agent and preparation method thereof, electroplating solution and application thereof, electroplating method of circuit board and circuit board

Info

Publication number: CN111020649B
Application number: CN201911299886.3A
Authority: CN
Inventors: 张二航
Original assignee: Dongguan Kangmike Electronic Materials Co ltd
Current assignee: Dongguan Kangmike Electronic Materials Co ltd
Priority date: 2019-12-17
Filing date: 2019-12-17
Publication date: 2021-08-06
Anticipated expiration: 2039-12-17
Also published as: CN111020649A

Abstract

The invention provides a leveling agent and a preparation method thereof, electroplating solution and application thereof, an electroplating method of a circuit board and the circuit board, and belongs to the technical field of circuit boards. The leveling agent comprises the raw materials with the structural general formula as

And having

Of the general structural formula or a non-nitrogen-containing substance of a glycol diglycidyl ether, R₁To R₄Represents H or C_zH_2z+1，R₅And R₆Represents H or CH₃. The leveling agent is beneficial to improving the macro and micro distribution of the plating layer, so that the thickness distribution of the plating layer is uniform, the hole filling quality of the blind hole is improved, and scratches are reduced. The preparation method comprises the step of polymerizing the raw materials, and the method is simple and easy to operate. The electroplating solution containing the leveling agent has the effect of the leveling agent and can be used for circuit board electroplating, integrated circuit electroplating and the like. The electroplating method of the circuit board, which comprises the step of electroplating the circuit board by using the electroplating solution, is simple and easy to operate, is beneficial to improving the hole filling and deep plating capability of the circuit board, and the obtained circuit board has better performance.

Description

Leveling agent and preparation method thereof, electroplating solution and application thereof, electroplating method of circuit board and circuit board

Technical Field

The invention relates to the technical field of circuit boards, in particular to a leveling agent and a preparation method thereof, an electroplating solution and application thereof, an electroplating method of a circuit board and the circuit board.

Background

At present, with the miniaturization of electronic products and the greater and greater functions and processing capabilities, the requirements on Integrated Circuits (ICs) and circuit boards are higher and higher, that is, the circuit is developed towards High Density Interconnect (HDI): the line width and line spacing (L/S), and the diameters of the interconnected blind holes and through holes become smaller and smaller.

The appearance shape of the circuit and the hole is related to the quality and the yield of circuit signals in the circuit board manufacturing process. The appearance of the circuit and the hole is determined by the flatness of the plating layer, so that the excellent flatness is important to the quality, the subsequent circuit manufacturing process is directly influenced, and the yield is related.

At present, requirements of circuit board high-end high-density interconnection (HDI) circuit boards, carrier plates or similar carrier plates and the like on flatness are very strict, and additives in current electroplating liquid have limited efficacy and narrow process parameters, so that the yield of high-end HDI is low.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention comprises providing a leveling agent which is beneficial to improving the macro and micro distribution of a coating, enabling the thickness distribution of the coating to be uniform, improving the hole filling quality of blind holes and reducing scratches.

The second purpose of the invention comprises providing a preparation method of the leveling agent, which is simple and easy to operate.

The third purpose of the invention comprises providing an electroplating solution containing the leveling agent, which is beneficial to making the thickness of the plating layer uniformly distributed, improving the hole filling quality of blind holes and reducing scratches.

A fourth object of the present invention includes providing a use of the above-mentioned plating solution, for example, for circuit board plating and/or integrated circuit plating, etc.

A fifth object of the present invention includes providing a plating method of a wiring board for plating the wiring board with the above-mentioned plating solution, which is simple and easy to operate.

The sixth purpose of the invention comprises providing a circuit board obtained by electroplating by the electroplating method, wherein the circuit board has better comprehensive performance.

The technical problem to be solved by the invention is realized by adopting the following technical scheme:

the invention provides a leveling agent, which comprises diamine substances and non-nitrogen-containing substances as raw materials;

the structural general formula of diamine substances is

Wherein R is₁、R₂、R₃And R₄Independently of one another, H or C_zH_2z+1；

R₅And R₆Independently of one another, H or CH₃；

x and y are independently an integer from 0 to 8 and x + y is less than or equal to 8.

Non-nitrogen containing materials include glycol diglycidyl ethers or compounds having the general structural formula:

wherein n is an integer of 0 to 7, j is an integer of 1 to 9, R₇Represents H or C_zH_2z+1。

In addition, the invention also provides a preparation method of the leveling agent, which comprises the following steps:

the diamine species is polymerized with the non-nitrogen containing species.

In some alternatives, the diamine species is heated with the solvent prior to reacting with the non-nitrogen-containing species.

In some optional schemes, the heating is to heat the mixed solution of the diamine substance and the water to 50-100 ℃, preferably to 80-100 ℃.

In some alternatives, the reaction with the non-nitrogen containing substance is performed at 80-140 deg.C for 1-24h, more preferably at 80-120 deg.C for 3-6h, and most preferably for 5 h.

In addition, the invention also provides electroplating solution which comprises the leveling agent.

In addition, the invention also provides the application of the electroplating solution, such as the electroplating solution can be used in circuit board electroplating and/or integrated circuit electroplating;

in some alternatives, the plating solution is used for blind hole filling and/or through hole copper plating of the circuit board;

in some alternatives, the plating solution is used for blind via filling and/or via plating in integrated circuit wiring interconnects.

In addition, the invention also provides an electroplating method of the circuit board, which comprises the following steps: electroplating the circuit board by using the electroplating solution. Optionally, the diameter of the blind hole of the circuit board is less than or equal to 150 μm, the hole depth is less than 100 μm, and the aspect ratio is less than 1: 1.

In some optional schemes, before electroplating, the method further comprises the step of carrying out metallization treatment on blind holes and/or filled holes in the circuit board to be processed and forming a conductive layer.

In some alternatives, the plating is performed under 1.0-2.5ASD for 30-80min, preferably 1.5A for 55 min.

In some alternatives, a dc regulated power supply is used for electroplating.

In addition, the invention also provides a circuit board which is obtained by electroplating by the electroplating method of the circuit board.

In some alternatives, the thickness of the copper plating of the wiring board is less than 25 μm, preferably less than 18 μm.

In some alternatives, the hole-filling recession of the circuit board is less than 15 μm, preferably less than 10 μm.

In some alternatives, the through-hole throwing power of the wiring board is greater than 60%, preferably greater than 75%.

The leveling agent and the preparation method thereof, the electroplating solution and the application thereof, the electroplating method of the circuit board and the beneficial effects of the circuit board comprise:

the leveling agent is obtained by polymerizing the diamine substance and the non-nitrogen-containing substance, and is applied to circuit board electroplating and/or integrated circuit electroplating as one of components of electroplating solution, so that the micro distribution of pore filling quality, scratches and the like of a circuit board is favorably improved, and the macro plating layer thickness distribution is favorably improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

Fig. 1 is a diagram showing a first plating result of a circuit board provided in embodiment 3 of the present application;

FIG. 2 is a diagram showing a second plating result of a circuit board provided in embodiment 3 of the present application;

FIG. 3 is a graph showing a first plating result of a wiring board provided in comparative example 1 of the present application;

FIG. 4 is a graph showing a first plating result of a wiring board provided in comparative example 2 of the present application.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The leveling agent and the preparation method thereof, the electroplating solution and the application thereof, the electroplating method of the circuit board and the circuit board are specifically described below.

In the field of circuit boards, the flatness of the plating layer has a crucial influence on the quality of the product. The flatness is also distribution, and the distribution is divided into macroscopic distribution and microscopic distribution. Macro-distribution refers to the overall plating thickness uniformity of the wiring board during the electroplating process. The distribution uniformity is usually improved by equipment adjustment, but even with perfect equipment, the plate edges and the plate center, and the upper and lower parts of the plate are slightly different. The microscopic distribution refers to the flatness of a certain point on the surface of the plate, and generally refers to the flatness of micro blind holes: the size of the depression of the filled hole after electroplating or the height of the hole opening bulge determines the micro-flatness, and the larger the depression is, the higher the bulge is, the reliability of the subsequent process and the circuit is influenced; the more the depth plating capability of the through holes, namely the closer the thickness in the through holes is to the thickness of the plate surface, the better the distribution is; the micro-flatness also includes defects such as micro scratches, fingerprints and the like on the surface of the board, which have negative effects on the subsequent circuit manufacturing process and are related to the yield.

The components of the electroplating solution have important influence on the quality of the coating, which not only determines the hole filling quality of the blind hole, the micro distribution of scratches and the like, but also has important influence on the thickness distribution of the macro coating. The inventors have made extensive studies and have proposed the following means.

The leveling agent is mainly used in electroplating liquid, and raw materials of the leveling agent comprise diamine substances and non-nitrogen-containing substances.

The structural general formula of the diamine substance is

Wherein R is₁、R₂、R₃And R₄Independently of one another, H or C_zH_2z+1；R₅And R₆Independently of one another, H or CH₃(ii) a x and y are, independently of each other, an integer from 0 to 8 (e.g., 0, 1,2, 3, 4, 5, 6, 7, or 8) and x + y is less than or equal to 8.

In some embodiments, the diamine species may include, for example, at least one of N, N-dimethyl-1, 4-butanediamine, 2-methylpentanediamine, 1, 8-octanediamine, N ' -octamethylenebisdichloroacetamide, N ' -dimethyl-1, 4-butanediamine, N ' -tetramethyl-1, 6-hexanediamine, 5- (diethylamino) pentanamine, and N, N-diisopropyl-1, 5-pentanediamine.

The non-nitrogen-containing substance can comprise glycol diglycidyl ether substances and also comprise substances with the following structural general formula:

wherein n is an integer from 0 to 7 (e.g., 0, 1,2, 3, 4, 5, 6, and 7), and j is an integer from 1 to 9 (e.g., 1,2, 3, 4, 5, 6, 7, 8, or 9). The diol diglycidyl ether may include at least one of 1,2,9, 10-diglycidyl decane, 1, 2-cyclohexanediol diglycidyl ether, poly (propylene glycol) diglycidyl ether, glycerol triglycidyl ether, 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like, for example.

By reference, non-nitrogen-containing species in the present application may include, for example, non-nitrogen-containing epoxies and/or non-nitrogen-containing acids. The non-nitrogen-containing epoxy may include at least one of 1, 7-octadiene diepoxy compound, 1,2,9, 10-diepoxydedecane, 1, 2-cyclohexanediol diglycidyl ether, poly (propylene glycol) diglycidyl ether, glycerol triglycidyl ether, 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like. The non-nitrogen-containing acid may include, for example, at least one of oxalic acid, 3-methylpentene diacid, adipic acid, methylsuccinic acid, 3-methyladipic acid, and the like. In addition, other types of non-nitrogen-containing species may be included, but in view of overall cost, the non-nitrogen-containing species preferably contain only non-nitrogen-containing epoxy and/or non-nitrogen-containing acid, i.e., the non-nitrogen-containing species may contain only non-nitrogen-containing epoxy, may contain only non-nitrogen-containing acid, or may contain both non-nitrogen-containing epoxy and non-nitrogen-containing acid. When the non-nitrogen-containing substance contains both the non-nitrogen-containing epoxy and the non-nitrogen-containing acid, the molar ratio of the non-nitrogen-containing epoxy to the non-nitrogen-containing acid is not particularly limited.

In some embodiments, the leveling agent may contain the diamine-based substance and the non-nitrogen-containing substance in a mass ratio of 0.5:1 to 1: 0.5.

In some embodiments, the molecular weight of the leveling agent can be 500-. Preferably 5000-.

The leveling agent provided by the application contains the diamine substances and the non-nitrogenous substances at the same time, and the substances are subjected to polymerization reaction, so that the final product is not only favorable for improving the pore filling quality, scratches and other micro-distribution of a circuit board, but also favorable for improving the thickness distribution of a macro-plating layer.

In addition, the application also provides a preparation method of the leveling agent, and the preparation method can comprise the following steps:

polymerizing the diamine-based substance and the non-nitrogen-containing substance.

In practice, for example, the diamine-based material may be heated with a solvent (e.g., water) and the heated material may then be reacted with the non-nitrogen-containing material. The diamine substance is heated firstly according to the sequence and then polymerized with the non-nitrogen-containing substance, so that the polymerization speed can be effectively controlled, and the phenomenon that the diamine substance and the non-nitrogen-containing substance react too fast to cause gel is avoided.

In some embodiments, the heating can be carried out by heating the mixture of diamine and water to 50-100 deg.C (e.g., 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C or 100 deg.C), preferably 80-100 deg.C. The heating may be, but not limited to, an oil bath. The non-nitrogen containing species are added slowly by controlling the temperature to 50-100 c instead of above 100 c. The addition sequence of the substances is combined, so that the speed of the polymerization reaction can be further effectively controlled, and the gel caused by violent reaction or over-quick reaction is avoided.

In some embodiments, the non-nitrogen containing substance may be added before refluxing at 80-140 deg.C (e.g., 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, etc.) for 1-24 h. In some preferred embodiments, the reaction with the non-nitrogen containing species may be refluxed at 80-120 ℃ for 3-6 hours, preferably 5 hours.

In some embodiments, the polymerizing may comprise: mixing diamine substances with an aqueous solution, and heating to 100 ℃ in an oil bath; slowly adding non-nitrogen-containing substances (non-nitrogen-containing epoxy and/or non-nitrogen-containing acid) after the temperature is stable; heating to about 110-120 deg.C and maintaining, refluxing for five hours; the oil bath was then cooled to about ambient temperature and the product was collected and analyzed to determine the concentration of the product.

Further, purification may be accomplished by means including, but not limited to, chromatography, which facilitates a relatively focused molecular weight and high purity of the purified product.

The preparation method of the leveling agent is simple, convenient to operate and beneficial to industrial production.

In addition, the application also provides an electroplating solution, which comprises the leveling agent.

Furthermore, the plating solution can also comprise an organic additive, and the organic additive comprises at least one of a gloss agent, a wetting agent and a stabilizer.

By reference, the gloss agent includes sulfur-containing organics. In some embodiments, the gloss agent molecule ends with the following functional groups: -SO₃Na or-SO₃H. In other embodiments, the gloss agent comprises the following molecular fragments in the molecule (i.e., not in the head-to-tail positions of the molecule): -S-S-or

Wherein R is₁Represents CH₂S or O.

In some preferred embodiments, the gloss agent contains-SO in addition to the molecular terminals₃Na or-SO₃In addition to H, it also contains-S-or

R₁Represents CH₂S or O.

Alternatively, the gloss agent used in the present application may include, for example, at least one of sodium 2, 3-dimercaptopropane sulfonate, sodium polydithiopropane sulfonate, 3- (benzoyl disulfide) -propyl sulfonic acid, sodium 3- (benzamide-sulfuric acid) propyl sulfonic acid, and the like.

In some embodiments, the gloss agent used has a molecular weight of no greater than 1000, preferably 200-1000. It is worth to say that the gloss agent with too large molecular weight is not suitable for adsorption at narrow hole angles such as the bottom corners of blind holes, and is not beneficial to exerting the effect of accelerating copper deposition.

In some preferred embodiments, the concentration of the gloss agent in the plating solution can be from 0.1 to 100mg/L, such as 0.1mg/L, 1mg/L, 5mg/L, 10mg/L, 50mg/L, or 100mg/L, etc., more preferably from 0.5 to 30mg/L, such as 0.5mg/L, 1mg/L, 2mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L, 25mg/L, or 30mg/L, etc.

In addition, the electroplating solution containing the brightener can accelerate the deposition of copper and achieve the effects of fine crystals and bright surface.

The wetting agent may, for example, include at least one of an ether, a fat and an alcohol.

In some embodiments, the wetting agent comprises an ethylene oxide/propylene oxide block polymer (EO/PO block polymer), wherein the molar ratio of ethylene oxide to propylene oxide can be 10:90, and other molar ratios can be used, and is not particularly limited herein.

As an alternative, the wetting agent used in the present application may include, for example, at least one of polyethylene glycol, polyethylene glycol propylene glycol copolymer, polyethylene glycol, polyethylene glyme, and polypropylene glycol.

In some embodiments, the wetting agent can have a molecular weight of 500-.

In some embodiments, the wetting agent can be present in the plating solution at a concentration of 0.1 to 4g/L, such as 0.1g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L, or 5g/L, etc., preferably 0.5 to 2 g/L.

The electroplating solution containing the wetting agent can wet the plate surface, help other additives to adsorb, and inhibit copper deposition to a certain extent.

By reference, the stabilizer may include formaldehyde. The concentration of formaldehyde in the plating solution may be 10-100mg/L, such as 10mg/L, 20mg/L, 50mg/L, 80mg/L, or 100 mg/L.

The formaldehyde contained in the electroplating solution can inhibit the formation of byproducts, has positive effect on improving the stability of the additive, and can prevent the additive and the electroplating solution from breeding bacteria. It is worth noting that formaldehyde is not present in the plating bath in excess, thereby preventing formaldehyde from adversely affecting the copper plating.

Further, the plating solution may further include an inorganic component, and the inorganic component may include Cu²⁺Providing object, conductive medium and Cl^-At least one of the provisions.

Alternatively, Cu²⁺The donor may include copper sulfate, preferably copper sulfate pentahydrate. Cu²⁺The donor serves primarily to provide copper ions in the plating bath.

In some embodiments, the concentration of the copper sulfate pentahydrate in the plating solution can be 120-270g/L, such as 120g/L, 150g/L, 180g/L, 200g/L, 220g/L, 250g/L, 270g/L, etc. Preferably, the concentration of the copper sulfate pentahydrate in the plating solution may be 200-250 g/L.

As a reference, the supply of the conductive medium may include sulfuric acid. The primary function of the supply of the conductive medium in the electroplating bath is to supply the conductive medium.

In some embodiments, the concentration of sulfuric acid in the plating solution can be 30-150g/L, such as 30g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L, or the like. Preferably, the concentration of sulfuric acid in the plating solution may be 40 to 80 g/L.

Referable to, Cl^-The supply of (a) may comprise sodium chloride or hydrochloric acid. Cl^-The main function of the donor in the electroplating solution is to supply chloride ions.

In some embodiments, the concentration of hydrochloric acid in the electroplating solution can be 30-150mL/L, such as 30mL/L, 50mL/L, 80mL/L, 100mL/L, 120mL/L, 150mL/L, or the like. In some more preferred embodiments, the concentration of hydrochloric acid in the electroplating solution can be 40-100mL/L, such as 40mL/L, 50mL/L, 80mL/L, or 100mL/L, among others.

The inorganic component may also include iron ion pairs and/or Mn, as referenced²⁺。

Wherein the iron ion pair comprises Fe²⁺And Fe³⁺. The supply of ferric ion pairs may comprise ferrous sulphate, the primary role of which is to supply ferrous ions, and/or ferric sulphate, the primary role of which is to supply ferric ions. The supply of the iron ion pair can stabilize and reduce the consumption of the gloss agent in the electroplating solution, even participate in a copper dissolution mechanism and reduce the thickness of copper plating.

In some embodiments Fe²⁺/Fe³⁺The total concentration in the plating solution may be 1-300mg/L, such as 10mg/L, 20mg/L, 40mg/L, 80mg/L, 160mg/L, 200mg/L, 250mg/L, or 300mg/L, and the like.

Referably, Mn²⁺The donor may include manganese sulfate, Mn²⁺One of the functions of the providing object in the electroplating solution is to provide manganese ions, the effect of the providing object is similar to the effect of iron ion pairs, the consumption of the gloss agent can be reduced, and the bath solution is more stable.

In some embodiments, Mn²⁺The concentration in the plating solution may be 1-30mg/L, such as 1mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L, 25mg/L, or 30 mg/L.

Bearing, above-mentioned plating solution is favorable to improving the microcosmic distribution such as pore-filling quality and mar of circuit board, still is favorable to improving macroscopic cladding material thickness distribution simultaneously.

Further, the application also provides the application of the electroplating solution, such as the electroplating of circuit boards and/or integrated circuits.

In some embodiments, the plating solution can be used for blind via filling and/or through via plating of circuit boards. In other embodiments, the plating solution can be used for blind via filling and/or via plating in integrated circuit line interconnects.

By using the electroplating solution in the technology, the hole filling quality, scratch and other micro-distribution of the circuit board can be effectively improved, and meanwhile, the thickness distribution of a macro-plating layer can also be effectively improved.

Further, the present application also provides a method for electroplating a circuit board, which may include the following steps: electroplating the circuit board by using the electroplating solution.

In some embodiments, the plating may be treated at 1.0-2.5ASD for 30-80 min. In one embodiment, the plating may be treated under 1.5ASD for 55 min.

Preferably, before electroplating, the method further comprises the step of metalizing the blind holes and/or filled holes in the circuit board to be processed and forming a conductive layer. The blind holes are, by reference, 150 μm or less in diameter, 100 μm less in depth and 1:1 less in aspect ratio.

In some embodiments, the plating lines used for plating include gantry lines, vertical continuous plating lines, or horizontal plating lines, and in the case of high-end high-density interconnect boards, vertical continuous plating lines or horizontal plating lines are preferred; the power supply used for electroplating comprises a direct current power supply or a positive and negative pulse power supply, and in the case of a high-end high-density interconnection circuit board, a direct current stabilized power supply is preferred.

It should be noted that other devices and operation flows for electroplating, which are not mentioned above, can refer to the prior art and are not described herein.

Furthermore, the application also provides a circuit board which is obtained by electroplating through the circuit board electroplating method.

In some embodiments, the copper plating thickness of the wiring board is less than 25 μm, preferably less than 18 μm;

in some embodiments, the via-filling recess of the wiring board is less than 15 μm, preferably less than 10 μm;

in some embodiments, the through-hole throwing power of the wiring board is greater than 60%, preferably greater than 75%.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

This example provides a leveling agent, which is prepared by the following method:

adding 2g of N, N-dimethyl-1, 4-butanediamine into a 50mL round-neck flask, adding 5g of water into the flask, and stirring; placing and fixing the flask in an oil bath, and installing a condensation reflux pipe on the flask; the oil bath was heated to 95 ℃ and then 2.45g of 1, 7-octadiene diepoxy compound were slowly added; after the filling is finished, raising the temperature of the oil bath to 115 ℃ and keeping the temperature for five hours; turning off heating and continuing stirring; cool to room temperature and collect the product as a tan. Purifying and drying the product to obtain white powder, namely the leveling agent.

Example 2

This example provides an electroplating bath comprising the following components: copper sulfate pentahydrate, sulfuric acid, hydrochloric acid, a gloss agent, a wetting agent and a leveling agent.

Wherein the concentration of the blue vitriol is 220 g/L; the concentration of the sulfuric acid is 50 g/L; the concentration of the hydrochloric acid is 50 mg/L; the gloss agent is sodium polydithio-dipropyl sulfonate, and the concentration of the gloss agent is 7 mg/L; the wetting agent is PEG6000, and the concentration of the wetting agent is 700 mg/L; the leveling agent is the leveling agent provided in example 1, and the concentration of the leveling agent is 40 mg/L.

Example 3

The present embodiment provides a circuit board, which is obtained by electroplating through the following hole-filling steps:

the size of the test plate is 5cm by 15cm, the plate thickness is 0.45mm, the size of the blind hole is 100 mu m in diameter, and the depth is 60 mu m; the via diameter was 200 μm and the aspect ratio was 2.25: 1.

Before chemical plating, the test panels were immersed in an oil removal tank for 2min, then rinsed in a water wash tank for 2min, and then immersed in an acid dip tank for 1 min. Wherein, the oil removing groove contains 5vt percent of oil removing agent and 5vt percent of sulfuric acid, and the rest is water. The acid leaching tank contains 5vt percent of sulfuric acid and the balance of water.

The plating solution provided in example 2 was added to a harlin tank, anodes were installed, a power supply positive wire was connected to both anodes, and the gas was turned on and stirred.

And (3) carrying out chemical plating on the test board soaked in the acid leaching tank on the Anmet horizontal copper wire (marking the mark on the board): and (3) putting the test board soaked in the acid leaching tank into a Harlin tank, connecting a cathode wire, turning on a power supply, plating for 50min by using 1.5A (about 1.5ASD), and washing, resisting oxidation, washing and drying after plating.

The electroplating bath is a Harlin bath (1.5L); the anode was an insoluble anode (brand DENORA) of size 5cm by 15cm and packed into an anode strip, 2 sheets; and a direct current power supply (0-10V).

And (3) carrying out electroplating analysis on the circuit board:

sampling on a plate, and preparing slices by using epoxy resin;

grinding the hole center by a grinder and polishing to ensure no scratch;

observing and recording the slice plating data by a metallographic microscope;

and a cyclic potential analyzer CVS (ECI) for analyzing the concentration of the gloss agent after the electroplating is finished, wherein the residual concentration of the gloss agent in the bath solution is 2.5 mg/L.

The results show that: the resulting wiring board had a copper plating thickness of 14 μm, a cavity filling of 2 μm (as shown in FIG. 1), and a through-hole throwing power of 80% (as shown in FIG. 2), indicating that the hole-filling and throwing powers achieved the predetermined results.

Example 4

This example provides a plating solution which differs from the plating solution of example 2 only in that: the concentration of the leveling agent is 100 mg/L.

Example 5

This example provides a circuit board, the plating parameters and the slicing procedure of the circuit board are the same as those of example 3, the only difference is that the plating solution in the harlin tank is the plating solution provided in example 4.

And (3) carrying out electroplating analysis on the electroplated circuit board, wherein the result shows that: the copper plating thickness of the obtained circuit board is 14 micrometers, the hole filling depression is less than 5 micrometers, and the through hole deep plating capacity is 81%, which indicates that the hole filling and deep plating capacities reach preset results.

Example 6

In example 2, another component was added to the plating bath composition: ferrous sulfate to Fe²⁺The concentration of (A) is up to 10 mg/L. The remaining concentration of the gloss agent analyzed after completion of the copper electroplating was 3.2 mg/L. The iron ions can reduce the consumption of the gloss agent and keep the concentration of the gloss agent relatively stable.

The thickness of copper plating of the circuit board is 14 μm, the hole filling depression is less than 5 μm, the deep plating capacity of the through hole is 80%, and the performance is consistent with that of the previous example.

Comparative example 1

This comparative example provides a circuit board, the electroplating parameters and the slice fabrication procedure of which were the same as in example 3, the only difference being that the electroplating bath in the harlin bath consisted of the following components: copper sulfate pentahydrate, sulfuric acid, hydrochloric acid, a gloss agent, a wetting agent and a leveling agent.

Wherein the concentration of the blue vitriol is 220 g/L; the concentration of the sulfuric acid is 50 g/L; the concentration of the hydrochloric acid is 50 mg/L; the gloss agent is sodium polydithio-dipropyl sulfonate, and the concentration of the gloss agent is 7 mg/L; the wetting agent is PEG6000, and the concentration of the wetting agent is 700 mg/L; the concentration of the leveling agent is 25 mg/L.

Wherein the leveling agent is prepared by the following method:

adding 3g of aminobenzoic acid into a 50mL round-neck flask, adding 7g of ethanol into the flask, and stirring; placing and fixing the flask in an oil bath, and installing a condensation reflux pipe on the flask; the oil bath was heated to 80 ℃ and then 3.11g of 1, 7-octadiene diepoxy compound were slowly added; after the filling is finished, raising the temperature of the oil bath to 85 ℃ and keeping the temperature for 7 hours; turning off heating and continuing stirring; cooling to room temperature and collecting the product, namely the leveling agent.

And (3) carrying out electroplating analysis on the electroplated circuit board, wherein the result shows that: the filled hole of the obtained circuit board has no recess but has a bulge (as shown in fig. 3), which indicates that the nitrogen-containing molecule is in a five-membered ring or six-membered ring form and is a macromolecular product obtained by polymerizing a structure which plays a role in connecting with non-nitrogen, and the macromolecular product generally has stronger inhibition capability or stronger through hole deep plating capability, but has poorer smoothness and cannot meet the requirement of high-density interconnection of circuit boards on smoothness.

Comparative example 2

The levelling agent in this comparative example was formed by the polymerisation of 1, 12-diaminododecane with adipic acid in a molar ratio of 1:1 (i.e.x + y >8 in the general formula of the diamine structure).

The leveling agent is used for preparing electroplating solution. Wherein the concentration of the blue vitriol is 220 g/L; the concentration of the sulfuric acid is 50 g/L; the concentration of the hydrochloric acid is 50 mg/L; the gloss agent is sodium polydithio-dipropyl sulfonate, and the concentration of the gloss agent is 7 mg/L; the wetting agent is PEG6000, and the concentration of the wetting agent is 700 mg/L; the concentration of the leveling agent is 100 mg/L.

The results of the plating analysis of the plated circuit boards show (as shown in fig. 4): the thickness of the copper plating of the obtained circuit board is 15 mu m, and the hole filling depression is larger than 15 mu m, which shows that the hole filling capability does not reach the expected result. This may be due to the fact that the longer the carbon chain between the diamines, the less capable it is to flatten the molecule by polymerizing with the non-nitrogen-containing moiety.

Comparative example 3:

in this comparative example, the leveling agent was polymerized from N, N-dimethyl-1, 4-butanediamine and sebacic acid (N >7) in a molar ratio of 1: 1.

The results also show that the copper plating results are not as expected.

To sum up, the leveling agent that this application provided is favorable to improving the macro and the micro-distribution of cladding material, makes cladding material thickness distribution even, improves the porefilling quality of blind hole, reduces the mar. The preparation method of the leveling agent is simple and easy to operate. The electroplating solution containing the leveling agent is also beneficial to enabling the thickness of the plating layer to be uniformly distributed, improving the hole filling quality of the blind hole and reducing scratches. The electroplating solution can be used for circuit board electroplating, circuit board packaging, semiconductor preparation and the like. The electroplating method of the circuit board for electroplating the circuit board by using the electroplating solution is simple and easy to operate. The circuit board obtained by electroplating by the electroplating method has better comprehensive performance.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The leveling agent is characterized in that raw materials of the leveling agent comprise diamine substances and non-nitrogen-containing substances;

the structural general formula of the diamine substance is

；

R₅And R₆Independently of one another, H or CH₃；

x and y are independently an integer from 0 to 8 and x + y is less than or equal to 8;

the diamine substance is at least one selected from N, N-dimethyl-1, 4-butanediamine, 2-methylpentanediamine, 1, 8-octanediamine, N' -dimethyl-1, 4-butanediamine, 5- (diethylamino) pentamine and N, N-diisopropyl-1, 5-pentanediamine;

the non-nitrogen-containing substance is selected from at least one of 1, 7-octadiene diepoxy compound and 1,2,9, 10-diepoxy decane;

the preparation of the leveling agent comprises the following steps:

polymerizing the diamine-based species with the non-nitrogen-containing species; the polymerization is that the diamine substance and the solvent are heated and then react with the non-nitrogen-containing substance; heating the mixed solution of the diamine substance and water to 50-100 ℃; the reaction with the non-nitrogen-containing substance is carried out at 80-140 ℃ for 1-24h under reflux.

2. The leveling agent according to claim 1, wherein the molar ratio of the diamine-based species to the non-nitrogen-containing species is from 0.5:1 to 1: 0.5.

3. A method for preparing a levelling agent according to claim 1 or 2, characterized by the steps of:

polymerizing the diamine-based species with the non-nitrogen-containing species;

the polymerization is that the diamine substance and the solvent are heated and then react with the non-nitrogen-containing substance;

heating the mixed solution of the diamine substance and water to 50-100 ℃;

the reaction with the non-nitrogen-containing substance is carried out at 80-140 ℃ for 1-24h under reflux.

4. The method for preparing leveling agent according to claim 3, wherein the heating is carried out by heating the mixture of the diamine-based substance and water to 80 to 100 ℃.

5. The method for preparing leveling agent according to claim 3, wherein the reaction with the non-nitrogen-containing substance is performed at 80-120 ℃ for 3-6 hours under reflux.

6. The method for preparing leveling agent according to claim 5, wherein the reaction with the non-nitrogen-containing substance is performed at 80-120 ℃ for 5 hours under reflux.

7. The method for preparing a leveling agent according to claim 3, wherein the molecular weight of the leveling agent obtained by polymerization is 500-50000.

8. The method for preparing leveling agent according to claim 7, wherein the molecular weight of the leveling agent obtained by polymerization is 2000-.

9. An electroplating bath comprising the leveler of claim 1 or 2.

10. The electroplating bath as set forth in claim 9 further comprising an organic additive including at least one of a gloss agent, a wetting agent, and a stabilizer.

11. The electroplating bath as set forth in claim 10 wherein the gloss agent comprises a sulfur-containing material.

12. The plating solution as recited in claim 11, wherein said brightener molecule has the following functional group at the end:

or

。

13. The electroplating solution as set forth in claim 11, wherein the brightener further comprises the following molecular fragments:

or

Wherein R is₁Represents CH₂S or O.

14. The electroplating bath as recited in claim 13 wherein the brightener comprises at least one of sodium 2, 3-dimercaptopropane sulfonate, sodium polydithiopropane sulfonate, 3- (benzoyl disulfide) -propyl sulfonic acid, and sodium 3- (benzamide-sulfuric acid) propyl sulfonic acid.

15. The electroplating bath according to claim 14, wherein the brightener has a molecular weight of no greater than 1000.

16. The plating solution as recited in claim 15, wherein the brightener has a molecular weight of 200-1000.

17. The plating solution as set forth in claim 10, wherein the concentration of said brightener in said plating solution is from 0.1 to 100 mg/L.

18. The plating solution as recited in claim 17 wherein said brightener is present in said plating solution at a concentration of 0.5 to 50 mg/L.

19. The plating solution as recited in claim 18 wherein said brightener is present in said plating solution at a concentration of 0.5 to 30 mg/L.

20. The electroplating bath according to claim 10, wherein the wetting agent comprises at least one of an ether, a fat, and an alcohol.

21. The electroplating bath of claim 20, wherein the wetting agent comprises an ethylene oxide/propylene oxide block polymer.

22. The electroplating bath as set forth in claim 21 wherein said wetting agent comprises at least one of polyethylene glycol, polyethylene glycol propylene glycol copolymer, polyethylene glycol, polyethylene glyme, and polypropylene glycol.

23. The electroplating bath as recited in claim 22, wherein the wetting agent has a molecular weight of 500-50000.

24. The electroplating bath as recited in claim 23, wherein the wetting agent has a molecular weight of 1000-30000.

25. The electroplating bath as recited in claim 24, wherein the wetting agent has a molecular weight of 1000-.

26. The electroplating bath according to claim 10, wherein the wetting agent is present in the electroplating bath at a concentration of 0.1-4 g/L.

27. The electroplating bath according to claim 26, wherein the wetting agent is present in the electroplating bath at a concentration of 0.5-2 g/L.

28. The electroplating bath as recited in claim 10 wherein the stabilizer comprises formaldehyde.

29. The plating solution as recited in claim 28, wherein the concentration of said formaldehyde in said plating solution is in the range of 10 to 100 mg/L.

30. The electroplating bath as set forth in claim 10 further comprising an inorganic component comprising Cu²⁺Providing object, conductive medium and Cl^-At least one of the provisions.

31. The plating solution of claim 30, wherein the Cu²⁺The donator comprises copper sulfate pentahydrate.

32. The plating solution as recited in claim 31, wherein the concentration of copper sulfate pentahydrate in the plating solution is 270 g/L.

33. The plating solution as recited in claim 32, wherein the concentration of the copper sulfate pentahydrate in the plating solution is 200-250 g/L.

34. The electroplating bath as recited in claim 30 wherein the supply of conductive medium comprises sulfuric acid.

35. The plating solution of claim 34, wherein the concentration of sulfuric acid in the plating solution is from 30 to 150 g/L.

36. The plating solution of claim 35, wherein the concentration of said sulfuric acid in said plating solution is from 40 to 80 g/L.

37. The plating solution of claim 30, wherein the Cl is^-The provider includes sodium chloride or hydrochloric acid.

38. The plating solution as recited in claim 37, wherein the concentration of said hydrochloric acid in said plating solution is in the range of 30 to 150 mL/L.

39. The plating solution as recited in claim 38, wherein the concentration of said hydrochloric acid in said plating solution is in the range of 40 to 100 mL/L.

40. The electroplating bath according to claim 30, wherein the inorganic component further comprises an iron ion pair donor and/or Mn²⁺Providing an iron ion pair providing object comprising Fe²⁺Providing object and Fe³⁺Provided is a substance.

41. The electroplating bath as set forth in claim 40 wherein the Fe²⁺The providing substance comprises ferrous sulfate, the Fe³⁺The donor includes ferric sulfate.

42. The electroplating bath as set forth in claim 41 wherein Fe²⁺/Fe³⁺The total concentration in the plating solution is 1-300 mg/L.

43. The electroplating bath as set forth in claim 40In the presence of Mn²⁺The donator comprises manganese sulfate.

44. The electroplating bath as set forth in claim 43 wherein Mn is²⁺The concentration in the plating solution is 1-30 mg/L.

45. Use of the electroplating solution according to any one of claims 9 to 44 for circuit board plating and/or integrated circuit plating.

46. The use of claim 45, wherein the plating solution is used for blind hole filling and/or through hole copper plating of circuit boards.

47. The use of claim 46 wherein the plating solution is used for blind via filling and/or via plating in integrated circuit wiring interconnects.

48. A method for electroplating a circuit board is characterized by comprising the following steps: electroplating of a circuit board with an electroplating solution according to any one of claims 9 to 44.

49. The electroplating method of claim 48, wherein the blind via diameter of the wiring board is 150 μm or less, the via depth is less than 100 μm, and the aspect ratio is less than 1: 1.

50. The plating method as recited in claim 49, further comprising, before plating, metallizing the blind via and/or filled via in the wiring board to be processed and forming a conductive layer.

51. The plating method as recited in claim 50, wherein the plating is performed under a condition of 1.4 to 2.5ASD for 40 to 80 min.

52. The plating method as recited in claim 51, wherein the plating is performed under the condition of 1.5ASD for 55 min.

53. The electroplating method of claim 48, wherein the plating line used for electroplating is a vertical continuous plating line or a horizontal plating line.

54. The electroplating method of claim 53, wherein the power supply used for electroplating is a DC regulated power supply.

55. A wiring board plated by the plating method for the wiring board according to any one of claims 48 to 54.

56. The wiring board of claim 55, wherein the thickness of the copper plating of the wiring board is less than 25 μm.

57. The wiring board of claim 56, wherein the copper plated thickness of the wiring board is less than 18 μm.

58. The wiring board of claim 55, wherein the via-filling depression of the wiring board is less than 15 μm.

59. The wiring board of claim 58, wherein the circuit board has a via-fill recess of less than 10 μm.

60. The wiring board of claim 55, wherein the through hole throwing power of the wiring board is greater than 60%.

61. The wiring board of claim 60, wherein the through hole throwing power of the wiring board is greater than 75%.