阅读说明：本技术 一种沉铜组合物及沉铜方法 (Copper deposition composition and copper deposition method ) 是由 孙宇曦 曾庆明 于 2021-06-03 设计创作，主要内容包括：本发明属于镀铜技术领域,具体涉及一种沉铜组合物及沉铜方法。本技术方案中发明人通过选择合适和稳定剂,使在沉铜的过程沉铜稳定,避免了铜离子的聚集,使得在沉铜的过程中达到晶粒细化的目的,避免部分区域铜富集增长形成斑块,提高了沉铜的光亮度和均匀性,保证沉铜的致密性,避免铜层稀疏,避免部分区域沉铜厚度降低,甚至出现铜空洞的现象,提高沉铜层的机械性能。(The invention belongs to the technical field of copper plating, and particularly relates to a copper deposition composition and a copper deposition method. In the technical scheme, the inventor selects proper stabilizer to stabilize the copper deposition in the copper deposition process, thereby avoiding the aggregation of copper ions, achieving the purpose of grain refinement in the copper deposition process, avoiding the accumulation and growth of copper in partial areas to form patches, improving the brightness and uniformity of the copper deposition, ensuring the compactness of the copper deposition, avoiding the sparseness of copper layers, avoiding the reduction of the thickness of the copper deposition in partial areas and even the phenomenon of copper voids, and improving the mechanical performance of the copper deposition layer.)

1. A copper deposition composition, characterized by comprising at least a copper ion source, a stabilizer and water, wherein the molecular structure of the stabilizer is selected from at least one of the structure (I), the structure (II) or the structure (III);

wherein X in the structure (I) is selected from O, N and at least one of groups containing O or N atoms, Y, Z is respectively selected from C, H, O, N and groups containing C, H, O, N at least one atom;

A＝R₁-C-R₂＝B

(Ⅱ)

wherein A, B in the structure (II) are respectively selected from O, N and at least one of groups containing O or N atoms, R₁And R₂Conjugation occurs, and a heterocyclic structure can be formed;

R₃-S-R₄-M

(Ⅲ)

wherein M in the structure (III) is selected from one or more of carbonyl, aldehyde group, cyano, amido, sulfydryl, carboxyl and alkenyl, R₃And R₄One or more groups respectively selected from alkyl, alkylamino, amino, amido, carboxyl, hydroxyl, aldehyde group, cyano, sulfydryl and alkenyl.

2. The copper deposition composition of claim 1, wherein the stabilizer is present in the copper deposition composition in an amount of 1 to 50 ppm.

3. The copper deposition composition of claim 2, wherein the stabilizer is present in the copper deposition composition in an amount of 1 to 10 ppm.

4. The copper deposition composition according to any one of claims 1 to 3, wherein the pH is in the range of 11 to 13 at 30 to 35 ℃.

5. The electroless copper plating composition according to claim 4, wherein the pH is in the range of 12 to 13 at 30 to 35 ℃.

6. The electroless copper plating composition according to claim 1, wherein the source of copper ions is an inorganic copper compound and/or an organic copper compound.

7. The copper deposition composition of claim 6, wherein the inorganic copper compound is at least one selected from the group consisting of copper chloride, copper oxide, copper sulfate, basic copper carbonate, copper nitrate and copper sulfate pentahydrate.

8. The copper deposition composition of claim 1, further comprising a surfactant, wherein the surfactant is an anionic surfactant and/or a nonionic surfactant.

9. The copper deposition composition of claim 1, further comprising a reducing agent, wherein the reducing agent is an inorganic reducing agent and/or an organic reducing agent.

10. A method of copper deposition using the copper deposition composition according to any one of claims 1 to 9, comprising at least the steps of:

(1) carrying out one or more of treatment pretreatment of bulking, degumming, activation and reduction on the substrate;

(2) and placing the pretreated substrate in a copper deposition composition at the temperature of 30-35 ℃ for copper deposition.

Technical Field

The invention belongs to the technical field of copper plating, and particularly relates to a copper deposition composition and a copper deposition method.

Background

Printed Circuit Boards (PCBs), also known as printed circuit boards, are important electronic components, support for electronic components, and carriers for electrical interconnection of electronic components. It is called a printed circuit board because it is made by electronic printing. The hole metallization of the printed circuit board is one of the core processes of the PCB manufacturing, and its main function is to form a conductive film by depositing metal copper or adsorbing conductive substances, so as to realize the electrical connection between the layers. Currently, the most mature via metallization is the deposition of base metal copper in the form of electroless copper deposition, in preparation for electrical conduction for subsequent electroplating.

In the prior art, a horizontal copper deposition liquid medicine is usually used for adjusting a copper deposition process, and the horizontal copper deposition liquid medicine is difficult to research and develop as follows: the adhesion between the substrate and the metal film is affected by the components of the modifier, such as pH regulator, surfactant species, resulting in the limitation of the copper electroless deposition on the substrate to the surface of the material; the activator adopts concentrated palladium liquid to realize copper deposition, and the problem of poor backlight quality is also caused while the cost pressure is increased; the efficiency and the service life of the reducing agent are low; the chemical copper deposition rate and the stability of the chemical copper deposition composition have a 'teeterboard' relationship, so that the chemical copper deposition composition is difficult to keep balance, and has a small operable window and the like. In order to overcome the development difficulty of the horizontal copper deposition, a regulator, an activating agent, a reducing agent and a chemical copper deposition composition need to be started. Chemical copper deposition is realized on the non-conductive substrate plate, and effective deposition of metal copper on the non-conductive substrate plate can be realized only after pretreatment work of conditioning substrate charges by using a chemical etching rough agent, adsorbing catalytic metal ions by using a cationic surfactant and reducing the catalytic metal ions by using a reducing substance is completed. After the substrate is roughened and hydrophilic undercut anchor points are formed, in order to achieve adhesion between the substrate and the catalytic metal ions, a modifier is usually added to adjust the adhesion, and the modifier is usually selected from surfactants, and the type of the surfactant is particularly important. The surfactant mainly reduces the surface tension of the solution, plays a role in wetting through holes and blind holes, and ensures the covering integrity of the catalytic metal in the holes. The surfactant is required to have a polar group structure which can be connected with the substrate, and can also play a role in adjusting the charge of the hole wall, so that the subsequent adsorption of metal ion palladium is facilitated. Most of the conventional regulators are based on cationic surfactants, but the number of polar groups of the cationic surfactants, such as N, O atom-containing groups, is limited.

The key of the electroless copper plating composition is that the copper plating rate is kept within a certain range through the component activity of the plating solution components, and meanwhile, the stability of the plating solution can ensure that the electroless copper plating can be continuously carried out. In general, the stability of the plating solution is maintained by adding an additive capable of forming a complex with monovalent copper generated during the reaction, such as cyanide and thiourea, but these substances are too stable, the stability constant of the formed complex is high, the ability to rob monovalent copper ions is very strong, free divalent copper ions in the solution are reduced, and copper deposition is suppressed. It is important to select a stabilizer with a low stability constant, such as bipyridyl, 1, 2-benzisothiazolin-3-one (BIT), 2-mercaptobenzimidazole carboxylic acid and the like, which forms a complex with monovalent copper, and to have an organic substance capable of wrapping the metal copper particles, which are side reaction products, in the stabilizer.

The copper deposition of electroless copper is not simply blanket and it is necessary to meet inspection requirements such as thermal stress testing, thermal shock testing, backlight testing, etc. Thus, the copper deposition of via metallization by horizontal copper deposition must achieve a high rate of effect. Therefore, the need to create a high-speed chemical deposition and low-palladium-catalyzed horizontal copper deposition solution requires improvement of the conditioning, activating, reducing and copper deposition compositions in the system, especially the screening of the components therein. The method has the advantages of low palladium matching, cost reduction, fine and smooth plating layer, stable plating solution and wide control window, and solves the difficulty in chemical copper deposition research and development.

Disclosure of Invention

In order to solve the above technical problems, the present invention provides, in a first aspect, a electroless copper plating composition comprising at least a source of copper ions, a stabilizer and water, wherein the molecular structure of the stabilizer is selected from at least one of structure (i), structure (ii) or structure (iii);

wherein X in the structure (I) is selected from O, N and at least one of groups containing O or N atoms, Y, Z is respectively selected from C, H, O, N and groups containing C, H, O, N at least one atom;

A＝R₁-C-R₂＝B

(Ⅱ)

wherein A, B in the structure (II) are respectively selected from O, N and at least one of groups containing O or N atoms, R₁And R₂Conjugation occurs, and a heterocyclic structure can be formed;

R₃-S-R₄-M

(Ⅲ)

wherein M in the structure (III) is selected from one or more of carbonyl, aldehyde group, cyano, amido, sulfydryl, carboxyl and alkenyl, R₃And R₄One or more groups respectively selected from alkyl, alkylamino, amino, amido, carboxyl, hydroxyl, aldehyde group, cyano, sulfydryl and alkenyl.

Preferably, the content of the stabilizing agent in the copper deposition composition is 1-50 ppm.

Preferably, the content of the stabilizing agent in the copper deposition composition is 1-10 ppm.

Preferably, the copper deposition composition has a pH range of 11-13.5 at 30-35 ℃.

Preferably, the copper deposition composition has a pH range of 12-13.5 at 30-35 ℃.

Preferably, the copper ion source is an inorganic copper compound and/or an organic copper compound.

Preferably, the inorganic copper compound is at least one selected from the group consisting of copper chloride, copper oxide, copper sulfate, basic copper carbonate, copper nitrate and copper sulfate pentahydrate.

Preferably, the copper deposition composition further comprises a surfactant, and the surfactant is an anionic surfactant and/or a nonionic surfactant.

Preferably, the copper deposition composition further comprises a reducing agent, and the reducing agent is an inorganic reducing agent and/or an organic reducing agent.

The second aspect of the invention provides a method for carrying out copper deposition on the copper deposition composition, which at least comprises the following steps:

(1) carrying out one or more of treatment pretreatment of bulking, degumming, activation and reduction on the substrate;

(2) and placing the pretreated substrate in a copper deposition composition at the temperature of 30-35 ℃ for copper deposition.

Has the advantages that: in the technical scheme, the inventor selects proper stabilizer to stabilize the copper deposition in the copper deposition process, thereby avoiding the aggregation of copper ions, achieving the purpose of grain refinement in the copper deposition process, avoiding the accumulation and growth of copper in partial areas to form patches, improving the brightness and uniformity of the copper deposition, ensuring the compactness of the copper deposition, avoiding the sparseness of copper layers, avoiding the reduction of the thickness of the copper deposition in partial areas and even the phenomenon of copper voids, and improving the mechanical performance of the copper deposition layer.

Drawings

FIG. 1 is a backlight picture of FR-4-TG140 in a copper deposition bath 33 in example 4;

FIG. 2 is a backlight picture of FR-4-TG140 in the copper deposition bath 34 in example 4;

FIG. 3 is a backlight picture of south Asia-IT 158 in the copper deposition bath 33 in example 4;

FIG. 4 is a backlight picture of south Asia-IT 158 in the copper deposition bath 34 in example 4;

fig. 5 is a backlight picture of korea-fighting mountain in the copper deposition bath 33 in example 4;

fig. 6 is a backlight picture of korea-fighting mountain in the copper deposition bath 34 in example 4;

FIG. 7 is a backlight picture of the growth benefit in example 4, S1150G, in a copper deposition bath 33

Fig. 8 is a backlight picture of the raw material of S1150G in the electroless copper plating bath 34 in example 4;

FIG. 9 is a photograph of the backlight of the copper deposition bath 33 of the example 4 combined metallocene-IT 158;

FIG. 10 is a photograph of the backlight of the copper deposition bath 34 containing the metallocene-IT 158 of example 4.

Detailed Description

For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

The meaning of the units therein is explained below: min: the method comprises the following steps of (1) taking minutes; ms: milliseconds; um: micron size; ppm: parts per million; ppb: parts per billion; DEG C: c, centigrade degree; g/L: g/l; a: ampere; dm: dividing the rice; DI: deionizing; wt%: the weight percentage is as follows; tg: glass transition temperature.

The first aspect of the invention provides a copper deposition composition, which at least comprises a copper ion source, a stabilizer and water, wherein the molecular structure of the stabilizer is selected from at least one of a structure (I), a structure (II) or a structure (III);

wherein X in the structure (I) is selected from O, N and at least one of groups containing O or N atoms, Y, Z is respectively selected from C, H, O, N and groups containing C, H, O, N at least one atom;

A＝R₁-C-R₂＝B

(Ⅱ)

wherein A, B in the structure (II) are respectively selected from O, N and at least one of groups containing O or N atoms, R₁And R₂Conjugation occurs, enabling the formation of heterocyclic structures, in which R₁And R₂The choice of (a) is not limited at all;

R₃-S-R₄-M

(Ⅲ)

wherein M in the structure (III) is selected from one or more of carbonyl, aldehyde group, cyano, amido, sulfydryl, carboxyl and alkenyl, R₃And R₄One or more groups respectively selected from alkyl, alkylamino, amino, amido, carboxyl, hydroxyl, aldehyde group, cyano, sulfydryl and alkenyl.

As a preferred embodiment, the heterocyclic ring-containing compound in the stabilizer includes, but is not limited to, biimidazoleBenzimidazole compounds1, 2-benzisothiazolin-3-one, thiabendazole, (9ci) -1H-benzimidazol-1-amineLevoimidazole base1,1' -sulfonyldiimidazoles2-mercaptobenzimidazole,Imidazo [1,2-b ]]Pyridazine1,1' -ethanediylbisimidazol, 3-methylpyrido [3,4-e]Benzoimidazol-2-amines1, 1-thiocarbonyldiimidazole2-mercaptobenzimidazole carboxylic acids5-ethoxy-2-mercaptobenzimidazole(-) -Benzotetramizole2-methylmercaptobenzimidazole, 3H-imidazo [4,5-b ]]Pyridine-5-carboxylic acid, 2-mercaptobenzimidazole carboxylic acid, 2 '-bipyridine-5, 5' -dimethanol, methylfurfuryl disulfide, 3- (2-pyridyldithio) propionic acid, difurfuryl disulfide and 2, 2-dithiodipyridine.

As a preferred embodiment, the non-heterocyclic compounds in the stabilizer include, but are not limited to, thiourea, lanthionine, ethyl thiooxamate, 2-mercapto-S-thiobenzoylacetic acid, S-carboxyethylisothiouronium betaine, thiosemicarbazideGuanidine sulfate, ethionamideAmidinothioureasThiopropionyl radicalAt least one of an amine, N-acetylthiourea, S-thiobenzoylthioglycolic acid and S-carboxyethylisothiouronium betaine.

As a preferable technical scheme, the content of the stabilizing agent in the copper deposition composition is 1-50 ppm.

As a preferable technical scheme, the content of the stabilizing agent in the copper deposition composition is 1-10 ppm.

The applicant finds in experiments that when the stabilizer with the structure of the application is used, rough deposition plaques can appear in copper deposition after copper deposition when the stabilizer is in a non-heterocyclic structure, and unexpectedly finds that when the stabilizer is in a non-heterocyclic structure, molecules contain S and at least 2 electron-donating groups, the generation of the deposition plaques in copper deposition can be effectively avoided, the applicant considers that the possible reason is that when the stabilizer contains S in molecules, molecular chains at two ends of an S atom extend into the copper deposition composition, a certain steric hindrance is formed at the moment, copper deposition on the surface of a substrate is hindered, the effect of refining copper grains is achieved, meanwhile, the compound can be comprehensively adjusted by combining at least 2 electron-donating groups to be coordinated with copper ions, the influence of the steric hindrance on complexing is reduced, copper deposition is stabilized, copper ion aggregation is avoided, and the purpose of grain refining is achieved in the copper deposition process, and the formation of plaque due to copper enrichment growth in partial areas is avoided. Particularly, when the stabilizer is in a non-heterocyclic structure, particularly lanthionine or S-carboxyethyl isothiourea betaine, the copper deposition has excellent brightness and uniformity.

As a preferable technical scheme, the pH value of the copper deposition composition is in the range of 11-13 at the temperature of 30-35 ℃.

As a preferable technical scheme, the pH value of the copper deposition composition is 12-13 at the temperature of 30-35 ℃.

In a preferred embodiment, the copper ion source is an inorganic copper compound and/or an organic copper compound.

As a preferable embodiment, the inorganic copper compound is at least one selected from the group consisting of copper chloride, copper oxide, copper sulfate, basic copper carbonate, copper nitrate and copper sulfate pentahydrate.

As a preferable technical scheme, the copper deposition composition further comprises a surfactant, and the surfactant is an anionic surfactant and/or a nonionic surfactant.

As a preferred embodiment, the anionic surfactant includes, but is not limited to, one of alkyl benzene sulfonate, alkyl or alkoxy naphthalene sulfonate, alkyl diphenyl ether sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenol ether sulfate, higher alcohol phosphate monoester, polyoxyalkylene alkyl ether phosphate (phosphate), and alkyl sulfosuccinate.

As a preferred technical solution, the nonionic surfactant includes, but is not limited to, one of polyethylene glycol, polyglycerol, polyoxyethylene ether, polyvinylpyrrolidone, condensate of alkylphenol and ethylene oxide (OP-10), fatty alcohol polyoxyethylene ether (AE0-9), polyvinyl alcohol, polyethylene glycol, and polyetheramine.

The copper deposition is the last step of horizontal copper deposition, and some buffering agents such as sodium citrate and disodium ethylene diamine tetraacetate are added in the copper deposition composition to maintain the stability of the pH value in the system, however, the applicant has found in experiments that when the substrate of the copper deposition is a glass epoxy plate, particularly when the Tg of the glass epoxy plate is at 140-, and only conventional sodium citrate or disodium ethylene diamine tetraacetate and the like are used, because the surfactant has strong wettability on a matrix, the complexation of copper ions is influenced, and at the same time when the components in the copper deposition composition are wetted on the matrix, a specific hard chain segment in the stabilizer breaks the influence brought by the surfactant or a longer soft chain segment structure extends into the copper deposition composition to ensure that the complexation of the copper ions is not influenced, so that the stabilizer can form a stable complex with the copper ions, the copper deposition composition is prevented from being decomposed and turning over a groove, the quality of a copper deposition layer is improved, and the service life of the copper deposition layer is prolonged.

In the copper deposition process, a surfactant is generally used for promoting the dispersibility of the components, and can be an anionic surfactant, a cationic surfactant or a nonionic surfactant, but the applicant finds that when the matrix in the application is a glass epoxy plate, particularly when the Tg of the glass epoxy plate is 180 ℃, a single surfactant is used, copper layers are sparse, the thickness of the deposited copper in a part of areas is reduced, the mechanical properties of the deposited copper are affected, and the like, and unexpectedly finds that when the anionic surface type surfactant and the nonionic surfactant are compounded, particularly the weight ratio is (1-10): 1, especially when the anionic surfactant is alkyl ether sulfonate and the nonionic surfactant is polyethylene glycol, and then when copper is deposited on a substrate with the Tg of 140-. The applicant has found that, in the present application, the action of the stabilizer and the specific surfactant can maintain the copper deposition rate at a certain level, even in the presence of the accelerator, the copper deposition rate is maintained at a level lower than 0.9um/h, the accelerator has a small influence on the copper deposition rate, and the phenomenon that the copper layer is burnt due to excessive addition of the accelerator caused by operation errors in experiments is avoided, the applicant believes that the possible reason is the composition of the stabilizer and the surfactant, and the long flexible chain segments in the specific nonionic surfactant and the anionic surfactant cause certain steric hindrance on the stabilizer with a specific structure towards the chain segments of the copper deposition composition while infiltrating the matrix, so that the reduction rate of copper ions complexed with the stabilizer is further hindered, and the influence of the accelerator on the copper deposition rate is reduced, the phenomenon of scorching caused by too fast copper deposition rate due to mistakenly adding too much accelerator is avoided.

As a preferred technical solution, the electroless copper plating composition further comprises a reducing agent, and the reducing agent is an inorganic reducing agent and/or an organic reducing agent.

As a preferred technical solution, the inorganic reducing agent includes but is not limited to one of sodium hypophosphite, boric acid and sodium borohydride.

As a preferred embodiment, the organic reducing agent includes, but is not limited to, one of formaldehyde, formaldehyde derivatives, dimethyl borane, shin, hydrazine, hydroxypropyl methylcellulose, sodium gluconate, glucuronolactone, sorbitol, sucrose, resorcinol, hydroquinone, catechol, hydroquinone, resorcinol, phenol sulfonic acid, cresol sulfonic acid, and hydroquinone sulfonic acid.

As a preferred technical scheme, the copper deposition composition also comprises an accelerator, and the accelerator comprises but is not limited to nickel acetylacetonate, nickel dibutyl dithiocarbamate and nickeloceneNickel acetylacetonate, nickel sulfamate (II)Nickel (II) oxalate dihydrateAmmonium nickel sulfate hexahydrate, nickel dimethylaminodithiocarbamateNickel diethyldithiocarbamatePyridones2-hydrazinopyridinesSulfazopyridines2-pyridineamides3-pyridinecarboxamidines3-pyridinethiourea2,2' -dipyridylamine4-methylaminopyridines2, 5-diaminopyridineAnd 3-amino-2-pyridonesOne kind of (1).

As a preferable technical scheme, the content of the accelerator in the copper deposition composition is 1-50 ppm.

As a preferable technical scheme, the content of the accelerator in the copper deposition composition is 1-20 ppm.

The second aspect of the invention provides a method for carrying out copper deposition on the copper deposition composition, which at least comprises the following steps:

(1) carrying out one or more of treatment pretreatment of bulking, degumming, activation and reduction on the substrate;

(2) and placing the pretreated substrate in a copper deposition composition at the temperature of 30-35 ℃ for copper deposition.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Example 1

In order to solve the above technical problems, the first aspect of the present embodiment provides 10 copper deposition baths, wherein the pH value of the copper deposition bath is 13 ± 0.2, and the bath is measured by a shanghai thunder magnetic pH meter, model: the PHS-3E test obtains the copper precipitation bath, namely the copper precipitation composition;

the copper precipitation bath comprises the following raw materials: wherein, A-copper sulfate pentahydrate; b-disodium ethylene diamine tetraacetate; c-sodium hydroxide; d-formaldehyde; nickel E-dimethylaminodithiocarbamate; f-water; G-1H-benzimidazol-1-amine; h-1,1' -oxalyldiimidazole; i-5-ethoxy-2-mercaptobenzimidazole; "/" indicates that the substance is not added, 5g/L sodium dodecyl diphenyl oxide disulfonate is added into each copper precipitation bath, 1g/L polyethylene glycol is added into each copper precipitation bath, the polyethylene glycol is PEG600, wherein the sodium dodecyl diphenyl oxide disulfonate and the polyethylene glycol are not listed in the table, and the addition amount of the other substances is shown in the table 1;

TABLE 1

A second aspect of this embodiment provides a method for performing copper deposition on a substrate, where the substrate in this embodiment is an FR-4 board, and the copper deposition is performed on a bare epoxy resin substrate of the FR-4 board, including the following steps:

(1) treating the substrate with a leavening agent at 80 deg.C for 6min, wherein the amount of the leavening agent is 240L, and then rinsing the substrate in tap water for 1min at room temperature, wherein the leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide, and the leavening agent is selected from SCC-A01H, Kangchong technologies, Inc.;

(2) treating the substrate in a degumming agent with the temperature of 80 ℃ for 12min, wherein the quantity of the degumming agent is 550L, the degumming agent is an aqueous solution of an alkaline oxidant with the pH value of 12, and then washing the substrate in tap water for 1min at room temperature, so as to enter the next procedure, wherein the degumming agent is selected from SCC-A02, SCG-A02;

(3) treating the substrate in a neutralizer at 50 deg.C for 1min, and washing the substrate in tap water at room temperature for 1min to obtain the next step, wherein the neutralizer is selected from SCC-A03H;

(4) weighing the substrate at room temperature, recording as m1, treating the substrate in a 50 ℃ conditioning agent for 1min, and then rinsing the substrate in tap water for 1min at room temperature, wherein the conditioning agent is selected from SCC-A04H of Guangdong Shuicheng science and technology Co., Ltd;

(5) treating the substrate in an activating solution at 50 ℃ for 45s, wherein the pH of the activating solution is about 9, and then soaking the substrate in tap water for 1min at room temperature to enter the next process, wherein the activating solution is selected from SCC-A06H of Guangdong Shuicheng science and technology limited;

(6) the substrate was treated for 35 seconds in a reducing agent at 35 ℃ in an amount of 180L and at a PH of about 9, the reducing agent being SCC-a07H from guangdong gmo technologies, inc.

(7) Different substrates were placed in a copper deposition bath 1-10 at 33 ℃ for electroless copper deposition for 30min, followed by rinsing the copper deposition plates with running tap water for 4min, drying each copper deposition plate with a blow dryer, weighing the copper deposition-finished substrates at room temperature, and recording as m 2.

The test method of the copper deposition rate comprises the following steps:

according to m1 and m2 obtained by weighing, the weight difference Δ m before and after the copper deposition on the base material is calculated to be m2-m 1. The laminate surface area S (25 cm)²) And copper deposition density ρ (8.92 g/cm)³) Calculating the copper deposition rate according to the electroless plating consumption time T and the formula speed V ═ Δ m/(S ×. rho ^ T), wherein the copper deposition bath 1-the copper deposition bath 1The copper deposition rate of the substrate in 0 is shown in Table 2.

TABLE 2

Wherein the copper deposition bath is abbreviated as bath, and the result is as follows:

from the above data, it can be seen that the inclusion of 1H-benzimidazol-1-amine, 1' -oxalyldiimidazole in the copper plating bath can stabilize the plating rate. At concentrations of 2.5ppm, 10ppm and 20ppm, the copper deposition plates of the copper plating baths containing 1H-benzimidazol-1-amine and 1,1' -oxalyldiimidazole appeared as bright and uniform plating layers. Copper chemically deposited from a bath containing 5-ethoxy-2-mercaptobenzimidazole exhibited bright and uniform areas with few rough deposited patches. The electroless copper deposition in the control bath showed large areas of irregular and rough black deposition with smaller bright deposition areas.

Example 2

In order to solve the above technical problems, the first aspect of this embodiment provides 9 copper deposition baths, wherein the pH value of the copper deposition bath is 13 ± 0.2, and the pH value is measured by a shanghai thunder magnetic pH meter, model: the PHS-3E test shows that the copper precipitation bath is the copper precipitation composition;

the copper precipitation bath comprises the following raw materials: wherein, A-copper sulfate pentahydrate; b-disodium ethylene diamine tetraacetate; c-sodium hydroxide; d-formaldehyde; nickel E-dimethylaminodithiocarbamate; f-water; g-thiooxamic acid ethyl ester; h-lanthionine; I-S-carboxyethyl isothiourea sugar beet; "/" indicates that the substance is not added, 5g/L sodium dodecyl diphenyl oxide disulfonate is added into each copper precipitation bath, 1g/L polyethylene glycol is added into each copper precipitation bath, the polyethylene glycol is PEG600, wherein the sodium dodecyl diphenyl oxide disulfonate and the polyethylene glycol are not listed in the table, and the addition amount of the other substances is shown in the table 3;

TABLE 3

A second aspect of this embodiment provides a method for performing copper deposition on a substrate, where the substrate in this embodiment is an FR-4 board, and the copper deposition is performed on a bare epoxy resin substrate of the FR-4 board, including the following steps:

(1) treating the substrate with a leavening agent at 80 deg.C for 6min, wherein the amount of the leavening agent is 240L, and then rinsing the substrate in tap water for 1min at room temperature, wherein the leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide, and the leavening agent is selected from SCC-A01H, Kangchong technologies, Inc.;

(2) treating the substrate in a degumming agent with the temperature of 80 ℃ for 12min, wherein the quantity of the degumming agent is 550L, the degumming agent is an aqueous solution of an alkaline oxidant with the pH value of 12, and then washing the substrate in tap water for 1min at room temperature, so as to enter the next procedure, wherein the degumming agent is selected from SCC-A02, SCG-A02;

(3) treating the substrate in a neutralizer at 50 deg.C for 1min, and washing the substrate in tap water at room temperature for 1min to obtain the next step, wherein the neutralizer is selected from SCC-A03H;

(4) weighing the substrate at room temperature, recording as m1, treating the substrate in a 50 ℃ conditioning agent for 1min, and then rinsing the substrate in tap water for 1min at room temperature, wherein the conditioning agent is selected from SCC-A04H of Guangdong Shuicheng science and technology Co., Ltd;

(5) treating the substrate in an activating solution at 50 ℃ for 45s, wherein the pH of the activating solution is about 9, and then soaking the substrate in tap water for 1min at room temperature to enter the next process, wherein the activating solution is selected from SCC-A06H of Guangdong Shuicheng science and technology limited;

(6) the substrate was treated in a reducing agent (180L) having a pH of about 9 at 35 ℃ for 35s, and then immersed in tap water at room temperature for 1min, and the next step was performed, wherein the reducing agent was selected from SCC-A07H of Guangdong Shuichi technologies, Inc.

(7) The different substrates were placed in a copper deposition bath 11-19 at 33 ℃ for electroless copper deposition for 30min, after which the copper deposition plates were rinsed for 4min with running tap water, and then each copper deposition plate was dried with a blow dryer, and the substrates after copper deposition were weighed again at room temperature and recorded as m 2.

The test method of the copper deposition rate comprises the following steps:

according to m1 and m2 obtained by weighing, the weight difference Δ m before and after the copper deposition on the base material is calculated to be m2-m 1. The laminate surface area S (25 cm)²) And copper deposition density ρ (8.92 g/cm)³) Calculating the copper deposition rate according to the electroless plating consumption time T and the formula speed V ═ Δ m/(S ×. rho ×. T), wherein the copper deposition rates of the base materials in the copper deposition bath 11-the copper deposition bath 19 are shown in Table 4.

TABLE 4

Wherein the copper deposition bath is abbreviated as bath, and the result is as follows:

the data show that the plating speed can be stabilized by the lanthionine, the S-carboxyethyl isothiourea betaine and the thiooxamic acid ethyl ester in the copper deposition bath, and the copper deposition speed standard of 0.4-0.6um/h in the industry is achieved. The plates deposited from the copper deposition bath containing lanthionine, S-carboxyethylisothiouronium betaine, are essentially bright and uniform. The plate surface containing the ethyl thiooxamate is dark in color and slightly rough.

Example 3

To solve the above technical problem, the first aspect of this embodiment provides 13 copper deposition baths, i.e. copper deposition compositions, wherein the pH value of the copper deposition bath is 13, and the pH value is measured by a shanghai thunder magnetic pH meter, model: PHS-3E is tested;

the copper precipitation bath comprises the following raw materials: wherein, A-copper sulfate pentahydrate; b-disodium ethylene diamine tetraacetate; c-sodium hydroxide; d-formaldehyde; nickel E-dimethylaminodithiocarbamate; f-water; g-1,1' -oxalyldiimidazole; h-lanthionine; I-S-carboxyethyl isothiourea sugar beet; j-5-ethoxy-2-mercaptobenzimidazole '/' represents that the substance is not added, 5g/L of sodium dodecyl diphenyl ether disulfonate is added into each copper precipitation bath, 1g/L of polyethylene glycol is added into each copper precipitation bath, the polyethylene glycol is PEG600, wherein the sodium dodecyl diphenyl ether disulfonate and the polyethylene glycol are not listed in the table, and the addition amount of the other substances is shown in the table 5;

TABLE 5

A second aspect of this embodiment provides a method for performing copper deposition on a substrate, where the substrate in this embodiment is an FR-4 board, and the copper deposition is performed on a bare epoxy resin substrate of the FR-4 board, including the following steps:

(1) treating the substrate with a leavening agent at 80 deg.C for 6min, wherein the amount of the leavening agent is 240L, and then rinsing the substrate in tap water for 1min at room temperature, wherein the leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide, and the leavening agent is selected from SCC-A01H, Kangchong technologies, Inc.;

(2) treating the substrate in a degumming agent with the temperature of 80 ℃ for 12min, wherein the quantity of the degumming agent is 550L, the degumming agent is an aqueous solution of an alkaline oxidant with the pH value of 12, and then washing the substrate in tap water for 1min at room temperature, so as to enter the next procedure, wherein the degumming agent is selected from SCC-A02, SCG-A02;

(3) treating the substrate in a neutralizer at 50 deg.C for 1min, and washing the substrate in tap water at room temperature for 1min to obtain the next step, wherein the neutralizer is selected from SCC-A03H;

(4) weighing the substrate at room temperature, recording as m1, treating the substrate in a 50 ℃ conditioning agent for 1min, and then rinsing the substrate in tap water for 1min at room temperature, wherein the conditioning agent is selected from SCC-A04H of Guangdong Shuicheng science and technology Co., Ltd;

(5) treating the substrate in an activating solution at 50 ℃ for 45s, wherein the pH of the activating solution is about 9, and then soaking the substrate in tap water for 1min at room temperature to enter the next process, wherein the activating solution is selected from SCC-A06H of Guangdong Shuicheng science and technology limited;

(6) the substrate was treated in a reducing agent (180L) having a pH of about 9 at 35 ℃ for 35s, and then immersed in tap water at room temperature for 1min, and the next step was performed, wherein the reducing agent was selected from SCC-A07H of Guangdong Shuichi technologies, Inc.

(7) The different substrates were placed in a copper deposition bath 20-32 at 34 ℃ for electroless deposition of copper for 5min, after which the copper deposition plates were rinsed for 4min with running tap water, and then each copper deposition plate was dried with a blow dryer, and the substrates after copper deposition were weighed again at room temperature and recorded as m 2.

The test method of the copper deposition rate comprises the following steps:

according to m1 and m2 obtained by weighing, the weight difference Δ m before and after the copper deposition on the base material is calculated to be m2-m 1. The laminate surface area S (25 cm)²) And copper deposition density ρ (8.92 g/cm)³) Calculating the copper deposition rate according to the electroless plating consumption time T and the formula speed V ═ Δ m/(S ×. rho ×. T), wherein the copper deposition rates of the base materials in the copper deposition bath 20-32 are shown in tables 6 and 7.

TABLE 6

Wherein the copper deposition bath is abbreviated as bath, and the result is as follows:

TABLE 7

Wherein the copper deposition bath is abbreviated as bath, and the result is as follows:

	bath 30	Bath 31	Bath 32
				Copper deposition rate (um/h)	0.68	0.60	0.88

Example 4

To solve the above technical problem, the first aspect of this embodiment provides 2 copper deposition baths, i.e. copper deposition compositions, wherein the pH value of the copper deposition bath at room temperature is 13, and the bath is measured by a shanghai thunder magnetic pH meter, model: PHS-3E is tested;

the copper precipitation bath comprises the following raw materials: wherein, A-copper sulfate pentahydrate; b-disodium ethylene diamine tetraacetate; c-sodium hydroxide; d-formaldehyde; nickel E-dibutyldithiocarbamate; nickel F-dimethylaminodithiocarbamate; g-ethoxy-2-mercaptobenzimidazole, H-lanthionine, I-water; "/" indicates that the substance is not added, 5g/L sodium dodecyl diphenyl oxide disulfonate is added into each copper precipitation bath, 1g/L polyethylene glycol is added into each copper precipitation bath, the polyethylene glycol is PEG600, wherein the sodium dodecyl diphenyl oxide disulfonate and the polyethylene glycol are not listed in the table, and the addition amount of the other substances is shown in the table 8;

TABLE 8

	Copper bath 33	Copper bath 34
			A	10g/L	10g/L
B	40g/L	40g/L
			C	8g/L	8g/L
D	4g/L	4g/L
			E	0.5ppm	/
F	/	0.5ppm
			G	10ppm	/
H	/	10ppm
			I	Balance of	Balance of

Five different FR/4 glass epoxy boards having a plurality of through holes were subjected to a copper deposition process using a copper deposition bath 33 and a copper deposition bath 34, FR-4-TG140, south asia-IT 158, korea-doushan, Sy-1150G, and bismuthal-IT 158, respectively, the FR-4-TG140 being obtained from taiwan integrated technology, the Sy-1150G being obtained from Shengyi, the bismuthal-IT 158 being obtained from bismuthal electronics corporation (ITEQ Corp), the south asia-IT 158 being obtained from south asia (NanYa), the korea-doushan being obtained from korea, and the glass epoxy boards having TG values ranging from 140 ℃ to 180 ℃. Each plate was 5cm x 10 cm.

The specific copper deposition steps are as follows:

(1) treating the substrate with a leavening agent at 80 deg.C for 6min, wherein the amount of the leavening agent is 240L, and then rinsing the substrate in tap water for 1min at room temperature, wherein the leavening agent is an aqueous solution containing 10 wt% propylene glycol ethyl ether and 35g/L sodium hydroxide, and the leavening agent is selected from SCC-A01H, Kangchong technologies, Inc.;

(2) treating the substrate in a degumming agent with the temperature of 80 ℃ for 12min, wherein the quantity of the degumming agent is 550L, the degumming agent is an aqueous solution of an alkaline oxidant with the pH value of 12, and then washing the substrate in tap water for 1min at room temperature, so as to enter the next procedure, wherein the degumming agent is selected from SCC-A02, SCG-A02;

(3) treating the substrate in a neutralizer at 50 deg.C for 1min, and washing the substrate in tap water at room temperature for 1min to obtain the next step, wherein the neutralizer is selected from SCC-A03H;

(4) weighing the substrate at room temperature, recording as m1, treating the substrate in a 50 ℃ conditioning agent selected from SCC-A04H of Guangdong Shuichi technologies, Inc. for 1min, and then rinsing the substrate in tap water at room temperature for 1 min;

(5) treating the substrate in an activating solution at 50 ℃ for 45s, wherein the pH of the activating solution is about 9, and then soaking the substrate in tap water for 1min at room temperature to enter the next process, wherein the activating solution is selected from SCC-A06H of Guangdong Shuicheng science and technology limited;

(6) the substrate was treated in a reducing agent (180L) having a pH of about 9 at 35 ℃ for 35s, and then immersed in tap water at room temperature for 1min, and the next step was performed, wherein the reducing agent was selected from SCC-A07H of Guangdong Shuichi technologies, Inc.

(7) The different substrates were placed in a copper deposition bath 33-34 at 34 ℃ for electroless copper deposition for 6min, followed by rinsing the copper deposition plates with running tap water for 4min, then drying each copper deposition plate with a blow dryer, weighing the copper deposition-finished substrates again at room temperature and recording as m 2.

Testing the backlight grade:

using a backlight processing method to check the copper deposition coverage condition of the substrate through hole wall:

each plate is traversed as close as possible to the center of the via to expose the sinker copper wall. A cross-section not more than 3mm thick from the center of the through-hole was taken from each panel and placed under a conventional optical microscope with 50X magnification with a light source placed behind the sample. The quality of the copper deposit is determined by the amount of visible light transmitted through the sample under the microscope. Within the plated through holes, the transmitted light is visible only in areas with incomplete electroless plating coverage. If there is no light projection and the cross section appears to be completely black, a rating of 10 on the backlit scale indicates complete copper coverage of the via walls. If the light passes through the entire area without any dark regions, it indicates that little to no copper metal is deposited on the via walls, and the cross section is rated 0. If the cross section has some dark areas as well as light areas, they are rated between 0 and 5. Each sheet was inspected for 10 through holes and rated for an average backlight rating recorded as a backlight rating. A backlight value of 7 and greater indicates that the copper deposition was acceptable, and the results are shown in Table 9.

The test method of the copper deposition rate comprises the following steps:

according to m1 and m2 obtained by weighing, the weight difference Δ m before and after the copper deposition on the base material is calculated to be m2-m 1. The laminate surface area S (25 cm)²) And copper deposition density ρ (8.92 g/cm)³) The electroless plating consumption time T, the formula speed V ═ Δ m/(S ×) ρ ×, T), the copper deposition rate was calculated, and the results of the copper deposition rate of the substrates in the copper deposition bath 33 to 34 are shown in table 9.

Wherein, the backlight picture of FR-4-TG140 in the copper deposition bath 33 is shown in figure 1, and the backlight picture of FR-4-TG140 in the copper deposition bath 34 is shown in figure 2; the backlight picture of the south Asia-IT 158 in the copper deposition bath 33 is shown in figure 3, and the backlight picture of the south Asia-IT 158 in the copper deposition bath 34 is shown in figure 4; the backlight picture of Korea-bucket mountain in the copper deposition bath 33 is shown in figure 5, and the backlight picture of Korea-bucket mountain in the copper deposition bath 34 is shown in figure 6; the backlight picture of Sy-1150G in the copper deposition bath 33 is shown in FIG. 7, and the backlight picture of Sy-1150G in the copper deposition bath 34 is shown in FIG. 8; the backlight picture of the linked metallocene-IT 158 in the copper deposition bath 33 is shown in figure 9, and the backlight picture of the linked metallocene-IT 158 in the copper deposition bath 34 is shown in figure 10, and the backlight picture of the copper deposition bath 33 and the copper deposition bath 34 can be seen to show extremely good backlight.

From the above data, it is understood that the present invention is only a preferred embodiment of the present invention, and not limited to other forms, and any person skilled in the art may change or modify the technical content disclosed in the above to equivalent embodiments with equivalent changes, but all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention do not depart from the technical content of the present invention, and still belong to the protection scope of the present invention.