Electroplating copper solution for ceramic package substrate and method of use thereof

Abstract

The application discloses a kind of electroplating copper solution for ceramic packaging substrate and its use method, it is related to circuit board electroplating technical field.The electroplating copper solution for ceramic packaging substrate includes the following mass concentration components: sulfuric acid 100-200g / L, copper sulfate pentahydrate 100-200g / L, chloride ion 50-80mg / L, accelerator 10-25mg / L, inhibitor 200-2000mg / L and leveling agent 10-20mg / L;The accelerator is 3-sulfur-isothiuron propyl sulfonate sodium compound.The application provides a kind of electroplating copper solution for ceramic packaging substrate and its use method, 3-sulfur-isothiuron propyl sulfonate sodium compound in electroplating copper solution can maintain better accelerator function when large current density electroplating, anode exists oxygen evolution case, octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether can be uniformly dispersed power line in relatively high temperature solution when large current density.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of circuit board electroplating, and particularly relates to a copper electroplating solution for ceramic packaging substrates and a use method thereof. BACKGROUND

[0002] LED is a semiconductor solid-state light-emitting device based on the PN junction electroluminescence principle. Different semiconductor materials can be used to prepare LED devices of different wavelengths. LED chip is a key device of LED. The quantum efficiency of ultraviolet LED chip is low, and it is easy to cause the chip to accumulate too much heat. If a large amount of heat is not discharged in time, the junction temperature of the LED will rise, and when the temperature exceeds the bearing temperature of the chip, the light-emitting efficiency of the LED will rapidly decrease, light decay will occur, and the emission spectrum will shift. When the junction temperature reaches 125℃ or above, the LED will even fail.

[0003] At present, the PN junction temperature is generally reduced from two aspects of reducing heat generation and accelerating heat dissipation. On the one hand, an AlN (aluminum nitride) buffer layer is introduced on the sapphire substrate, and an AlN / AlGaN (aluminum nitride / gallium nitride) superlattice structure is used to reduce the dislocation number of epitaxial material, improve the quantum efficiency, and reduce heat generation. On the other hand, flip-chip ultraviolet LED chips are manufactured, and flip-chip eutectic technology is used to directly bond the ultraviolet LED chips to a high-thermal-conductivity packaging substrate by eutectic bonding, so as to reduce the packaging interface thermal resistance, so that the heat generated by the chip can be effectively conducted to the packaging substrate, and the junction temperature of the ultraviolet LED is reduced.

[0004] In addition, since the ultraviolet LED chip is very sensitive to the external environment, it is easy to cause performance degradation or failure due to the invasion of water vapor and dust. Air-tight packaging is often used to effectively separate the chip from the surrounding environment, prevent the invasion of surrounding moisture during the working life, ensure the normal work of the chip, and make it obtain good long-term reliability, so it has become one of the important development directions of ultraviolet LED packaging.

[0005] At present, most ultraviolet LED packages generally use epoxy resin or silicone organic materials coated on the surface of the chip. This packaging structure is simple, the process is mature, and the cost is relatively low. However, it is difficult to ensure the reliability of the organic material working in high-intensity ultraviolet light, humidity and heat for a long time.

[0006] In order to solve the problems existing in the packaging of ultraviolet LED chips, firstly, inorganic material metal is used instead of organic material, then the ultraviolet LED chip is placed inside the metal dam structure, vacuum is extracted or inert gas is filled, and the quartz glass lens is used to realize airtight sealing, so that the reliability of the ultraviolet LED is improved. The ceramic packaging substrate has high line precision and high surface flatness, and can be prepared with a through hole, so as to meet the packaging requirements of flip chip, and therefore is the first choice for the packaging substrate of ultraviolet LED. In order to realize the airtight packaging of ultraviolet LED, a metal dam needs to be prepared on the plane ceramic packaging substrate, and the ceramic packaging substrate with the dam is also called three-dimensional ceramic packaging substrate. The dam preparation direction mainly includes two aspects: one is to process the dam into a shape of the dam by machining ceramic or metal materials, and then the dam and the plane packaging substrate are fixed together by means of gluing, welding and the like, so as to form a three-dimensional ceramic packaging substrate; the other is to directly prepare the dam structure on the plane packaging substrate, and there are technical solutions such as electroplating and inorganic slurry forming. The gluing process is simple, low in cost and easy for industrialized mass production. The disadvantage is that the organic glue will age continuously during use, and the reliability will be continuously reduced, especially in the case of sharp change of temperature or humidity. The dam is directly electroplated together with the LED ceramic packaging substrate, which is high in reliability, and the disadvantage is that the height of the dam is generally about 300 microns, and the conventional electroplating time is very long, which is more than ten hours, and the production efficiency is low.

[0007] In the process of electroplating the dam, under the condition that the thickness of the plating layer is required, the current density is inversely proportional to the electroplating time. If the electroplating time is shortened, the current density during electroplating needs to be increased, but the current density allowed by the existing copper electroplating additive is generally 5A / dm 2 At present, there is basically no high-speed copper electroplating additive with large current density specially used for the preparation of the dam of the LED packaging substrate, and the development of the copper electroplating solution for the ceramic packaging substrate and the use method thereof is an inevitable choice to adapt to the improvement of the production technology of special circuit boards in China. SUMMARY

[0008] The technical problem to be solved by the present application is to develop a high-speed copper electroplating solution with large current density for the preparation of the dam of the LED ceramic packaging substrate, to increase the working current density during electroplating, to shorten the electroplating time, and to make the product meet the requirements of 8-12A / dm 2 High current density high-speed copper plating requirements.

[0009] In view of the deficiencies in the prior art, the present application provides a copper electroplating solution for a ceramic packaging substrate and a use method thereof, and the use of a specific copper electroplating solution with suitable use parameters can effectively improve the working current density and improve the electroplating efficiency during the preparation of the dam.

[0010] Specifically includes the following technical solutions:

[0011] In a first aspect, a plating copper solution for ceramic packaging substrate is provided, comprising the following mass concentration components: sulfuric acid 100-200 g / L, copper sulfate pentahydrate 100-200 g / L, chloride ion 50-80 mg / L, accelerator 10-25 mg / L, inhibitor 200-2000 mg / L, and leveler 10-20 mg / L; the accelerator is a 3-sulfur-isothiuronium sodium propyl sulfonate compound, and the inhibitor is octylphenol polyoxyethylene ether and / or nonylphenol polyoxyethylene ether.

[0012] Specifically, the accelerator is C4H 10 N2O3S2.

[0013] Further, the leveler is 2-mercaptobenzimidazole or 2-mercaptobenzothiazole.

[0014] Further, the inhibitor is octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether, and the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether is 1:(0.5-2).

[0015] Further, the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether is 1:1.

[0016] Further, the plating copper solution for ceramic packaging substrate consists of the following mass concentration components: sulfuric acid 150-200 g / L, copper sulfate pentahydrate 100-150 g / L, chloride ion 50-80 mg / L, accelerator 10-25 mg / L, inhibitor 200-2000 mg / L, leveler 10-20 mg / L, and the balance is deionized water.

[0017] Further, the plating copper solution for ceramic packaging substrate consists of the following mass concentration components: sulfuric acid 150 g / L, copper sulfate pentahydrate 150 g / L, chloride ion 70 mg / L, accelerator 15 mg / L, inhibitor 1000 mg / L, leveler 15 mg / L, and the balance is deionized water.

[0018] In a second aspect, a use method of the plating copper solution for ceramic packaging substrate according to the first aspect is provided, comprising the following steps: using the plating copper solution for ceramic packaging substrate according to the first aspect to electroplate a product to be plated.

[0019] Preferably, the use method of the plating copper solution for ceramic packaging substrate comprises the following steps: using the plating copper solution for ceramic packaging substrate to electroplate a product to be plated by flowing the plating copper solution for ceramic packaging substrate through air blowing.

[0020] Further, the plating conditions are as follows: using a direct current power supply, the current density of the cathode is 8-12 A / dm2 .

[0021] Further, the temperature of the electroplating copper solution for the ceramic packaging substrate is 30-50℃.

[0022] Further, the anode of the electroplating is a titanium anode coated with iridium tantalum coating on the surface layer, and the cathode of the electroplating is the product to be electroplated.

[0023] The present application has the following beneficial effects:

[0024] The present application provides an electroplating copper solution for ceramic packaging substrate and a method for using the same. The 3-sulfur-isothiurea sodium propyl sulfonate compound in the electroplating copper solution can maintain good accelerator function under the condition of oxygen evolution of anode at large current density electroplating. The octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether can uniformly disperse electric lines at large current density in the solution at relatively high temperature (30-50℃). In addition, the accelerator, inhibitor and leveling agent in the electroplating copper solution and other components can work together to meet the requirements of 8-12A / dm 2 2 high-speed copper plating at large current density. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0026] Figure 1 The microscope image of the sample after appearance test of the sample of the present application example 1;

[0027] Figure 2 The microscope image of the sample after appearance test of the sample of the present application example 2;

[0028] Figure 3 The microscope image of the sample after appearance test of the sample of the present application example 3;

[0029] Figure 4 The microscope image of the sample after appearance test of the sample of the present application example 4;

[0030] Figure 5 The microscope image of the sample after appearance test of the sample of the present application example 5;

[0031] Figure 6 The microscope image of the sample after appearance test of the sample of the present application example 6;

[0032] Figure 7Microscope image of sample after sample appearance test for Example 7 of the invention;

[0033] Figure 8 Microscope image of sample after sample appearance test for Example 8 of the invention;

[0034] Figure 9 Microscope image of sample after sample appearance test for Example 9 of the invention;

[0035] Figure 10 Microscope image of sample after sample appearance test for Example 10 of the invention;

[0036] Figure 11 Microscope image of sample after sample appearance test for Example 11 of the invention;

[0037] Figure 12 Microscope image of sample after sample appearance test for Example 12 of the invention;

[0038] Figure 13 Microscope image of sample after sample appearance test for Example 13 of the invention;

[0039] Figure 14 Microscope image of sample after sample appearance test for Example 14 of the invention;

[0040] Figure 15 Microscope image of sample after sample appearance test for Example 15 of the invention;

[0041] Figure 16 Microscope image of sample after sample appearance test for Example 16 of the invention;

[0042] Figure 17 Microscope image of sample after sample appearance test for Comparative Example 1 of the invention;

[0043] Figure 18 Microscope image of sample after sample appearance test for Comparative Example 2 of the invention;

[0044] Figure 19 Microscope image of sample after sample appearance test for Comparative Example 3 of the invention;

[0045] Figure 20 Microscope image of sample after sample appearance test for Comparative Example 4 of the invention;

[0046] Figure 21 Microscope image of sample after sample appearance test for Comparative Example 5 of the invention;

[0047] Figure 22 Microscope image of sample after sample appearance test for Comparative Example 6 of the invention;

[0048] Figure 23 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 7;

[0049] Figure 24 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 8;

[0050] Figure 25 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 9;

[0051] Figure 26 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 10;

[0052] Figure 27 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 11;

[0053] Figure 28 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 12;

[0054] Figure 29 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 13;

[0055] Figure 30 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 14;

[0056] Figure 31 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 15;

[0057] Figure 32 Microscope image of the sample after performing the sample appearance test for Inventive Comparative Example 16. DETAILED DESCRIPTION

[0058] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0059] It should be understood that, when used in the specification and the appended claims, the terms "comprise" and "include" indicate the presence of the described features, integers, steps, operations, elements, and / or components, but do not exclude one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0060] It should also be understood that the terms used in the specification and the appended claims are intended to describe specific embodiments and do not intentionally limit the application. As used in the specification and the appended claims, the singular forms "a," "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0061] It should further be understood that the term "and / or" used in the specification and the appended claims, means one or more of the associated listed items as well as all possible combinations of the items.

[0062] In order to more fully understand the technical content of the present application, the technical solutions of the present application are further introduced and described below in combination with specific embodiments.

[0063] The preparation method of the electroplating copper solution for ceramic packaging substrate of the example and the comparative example comprises the following steps: mixing sulfuric acid, copper sulfate pentahydrate, chloride ions, an accelerator, an inhibitor, a leveling agent, and the rest of deionized water to prepare.

[0064] Example 1

[0065] An electroplating copper solution for ceramic packaging substrate, which is composed of the following mass concentration components: sulfuric acid 150 g / L, copper sulfate pentahydrate 150 g / L, chloride ions 70 mg / L, accelerator 15 mg / L, inhibitor 1000 mg / L, leveling agent 15 mg / L, and the rest of deionized water; the accelerator is a 3-sulfur-isothiuronium propyl sulfonic acid sodium compound (C4H 10 N2O3S2); the inhibitor is octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether, and the mass ratio of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether is 1:1; the leveling agent is 2-mercaptobenzimidazole.

[0066] The use method of the electroplating copper solution for ceramic packaging substrate comprises the following steps:

[0067] The electroplating copper solution for ceramic packaging substrate with a use temperature of 40°C is added to an electroplating tank, titanium anodes with an iridium tantalum coating on the surface layer are placed as anodes at both ends of the electroplating tank, agitation is performed by air blowing in the middle of the tank, the air input speed is 2 L / min, the ceramic packaging substrate electroplating copper solution is made to flow by air blowing, and the product to be electroplated is electroplated. The cathode for electroplating is the product to be electroplated. The conditions for electroplating are as follows: a direct current power supply is used, the current density of the cathode is 10 A / dm 2 .

[0068] The plating copper solution for ceramic packaging substrate of Examples 2-6 was prepared according to the components and the use method of the plating copper solution for ceramic packaging substrate in Table 1 below and plating was performed according to the use method. Table 1 shows the difference between Examples 2-6 and Example 1. The components and the use method of the plating copper solution for ceramic packaging substrate not mentioned in Table 1 are the same as those of Example 1.

[0069] Table 1 Components and use method of plating copper solution for ceramic packaging substrate of Examples 2-6

[0070]

[0071] wherein the accelerator in Table 1 is a 3-thio-isothiuronium sodium propyl sulfonate compound (C4H 10 N2O3S2), the inhibitor ratio is the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether, the leveler 1 is 2-mercaptobenzimidazole, and the leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature respectively refer to the plating conditions in the use method of the plating copper solution for ceramic packaging substrate and the temperature of the plating copper solution for ceramic packaging substrate.

[0072] The plating copper solution for ceramic packaging substrate of Examples 7-11 was prepared according to the components and the use method of the plating copper solution for ceramic packaging substrate in Table 2 below and plating was performed according to the use method. Table 2 shows the difference between Examples 7-11 and Example 1. The components and the use method of the plating copper solution for ceramic packaging substrate not mentioned in Table 2 are the same as those of Example 1.

[0073] Table 2 Components and use method of plating copper solution for ceramic packaging substrate of Examples 7-11

[0074]

[0075] wherein the accelerator in Table 2 is a 3-thio-isothiuronium sodium propyl sulfonate compound (C4H 10 N2O3S2), the inhibitor ratio is the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether, the leveler 1 is 2-mercaptobenzimidazole, and the leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature respectively refer to the plating conditions in the use method of the plating copper solution for ceramic packaging substrate and the temperature of the plating copper solution for ceramic packaging substrate.

[0076] The plating copper solution for ceramic packaging substrate of Examples 12-16 was prepared according to the components and the use method of the plating copper solution for ceramic packaging substrate in Table 3 below and plating was performed according to the use method. Table 3 shows the difference between Examples 12-16 and Example 1. The components and the use method of the plating copper solution for ceramic packaging substrate not mentioned in Table 3 are the same as those of Example 1.

[0077] Table 3. Composition and use method of electroplating copper solution for ceramic packaging substrate of Examples 12-16

[0078]

[0079] wherein the accelerator in Table 3 is a 3-thio-isothiuronium sodium propyl sulfonate compound (C4H 10 N2O3S2), the inhibitor ratio is the mass ratio of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether, the leveler 1 is 2-mercaptobenzimidazole, and the leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature respectively refer to the plating conditions in the use method of the electroplating copper solution for ceramic packaging substrate and the temperature of the electroplating copper solution for ceramic packaging substrate.

[0080] The electroplating copper solutions for ceramic packaging substrate of Comparative Examples 1-5 were prepared according to the composition and use method of the electroplating copper solution for ceramic packaging substrate in Table 4 below, and plating was performed according to the use method. Table 4 shows the differences between Comparative Examples 1-5 and Example 1. The composition and use method of the electroplating copper solution for ceramic packaging substrate not mentioned in the table are the same as those of Example 1.

[0081] Table 4. Composition and use method of electroplating copper solution for ceramic packaging substrate of Comparative Examples 1-5

[0082]

[0083] wherein the accelerator in Table 4 is a 3-thio-isothiuronium sodium propyl sulfonate compound (C4H 10 N2O3S2), the inhibitor ratio is the mass ratio of octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether, the leveler 1 is 2-mercaptobenzimidazole, and the leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature respectively refer to the plating conditions in the use method of the electroplating copper solution for ceramic packaging substrate and the temperature of the electroplating copper solution for ceramic packaging substrate.

[0084] The electroplating copper solutions for ceramic packaging substrate of Comparative Examples 6-10 were prepared according to the composition and use method of the electroplating copper solution for ceramic packaging substrate in Table 5 below, and plating was performed according to the use method. Table 5 shows the differences between Comparative Examples 6-10 and Example 1. The composition and use method of the electroplating copper solution for ceramic packaging substrate not mentioned in the table are the same as those of Example 1.

[0085] Table 5. Composition and use method of electroplating copper solution for ceramic packaging substrate of Comparative Examples 6-10

[0086]

[0087] wherein the accelerator in Table 5 is a 3-thio-isothiuronium sodium propyl sulfonate compound (C4H 10N2O3S2), the ratio of the inhibitors is the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether, leveler 1 is 2-mercaptobenzimidazole, and leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature refer to the plating conditions in the use method of the copper plating solution for ceramic packaging substrates and the temperature of the copper plating solution for ceramic packaging substrates, respectively.

[0088] The copper plating solutions for ceramic packaging substrates of Comparative Examples 11-16 were prepared according to the components and use method of the copper plating solution for ceramic packaging substrates in Table 6 below, and plating was performed according to the use method. Table 6 shows the differences between Comparative Examples 11-16 and Example 1. The components and use method of the copper plating solution for ceramic packaging substrates not mentioned in the table are the same as in Example 1.

[0089] Table 6 Components and use method of the copper plating solution for ceramic packaging substrates of Comparative Examples 11-16

[0090]

[0091] In Table 6, the accelerator is a 3-sulfur-isothiuronium propyl sulfonate sodium compound (C4H 10 N2O3S2), the ratio of the inhibitors is the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether, leveler 1 is 2-mercaptobenzimidazole, and leveler 2 is 2-mercaptobenzothiazole. The current density and the solution temperature refer to the plating conditions in the use method of the copper plating solution for ceramic packaging substrates and the temperature of the copper plating solution for ceramic packaging substrates, respectively. In Table 6, Comparative Example 15 and Comparative Example 16 use phosphor copper anodes as anodes.

[0092] Performance test:

[0093] I. Appearance test of samples: The product to be plated is a test plate to be plated, which is pretreated by oil removal, micro-etching, and activation in a dilute sulfuric acid solution, and then is placed in the liquid (the copper plating solution for ceramic packaging substrates of the example or the comparative example) of the above-mentioned plating tank, respectively, and is plated (vertically placed in the middle position of the plating tank) using the use method of the copper plating solution for ceramic packaging substrates of the example or the comparative example, until the plating layer thickness reaches 300 microns. The appearance and microscope observation of the plated sample are performed, and the sample is required to be uniform, bright, and flat in appearance, without pinholes and copper particles.

[0094] II. Tensile strength and elongation at break test: A stainless steel plate is used as the product to be plated instead of the test plate in the appearance test of samples, and the rest of the conditions are the same as in the appearance test of samples. The plating layer thickness is plated to 60 microns, and a copper foil is made by peeling off the stainless steel plate. The tensile strength and elongation at break test are performed using the copper foil. The tensile strength is greater than 248 MPa, and the elongation at break is greater than 10%, which is qualified.

[0095] The ceramic packaging substrates of Examples 1-5 were subjected to performance testing using a copper electroplating solution, and the results of the testing are shown in Table 7 below:

[0096] Table 7 Performance testing results of ceramic packaging substrates of Examples 1-5 using a copper electroplating solution

[0097]

[0098] Figure 1 Microscope image of the sample after performing sample appearance testing for Example 1 of the present application; Figure 2 Microscope image of the sample after performing sample appearance testing for Example 2 of the present application; Figure 3 Microscope image of the sample after performing sample appearance testing for Example 3 of the present application; Figure 4 Microscope image of the sample after performing sample appearance testing for Example 4 of the present application; Figure 5 Microscope image of the sample after performing sample appearance testing for Example 5 of the present application.

[0099] The ceramic packaging substrates of Examples 6-10 were subjected to performance testing using a copper electroplating solution, and the results of the testing are shown in Table 8 below:

[0100] Table 8 Performance testing results of ceramic packaging substrates of Examples 6-10 using a copper electroplating solution

[0101]

[0102] Figure 6 Microscope image of the sample after performing sample appearance testing for Example 6 of the present application; Figure 7 Microscope image of the sample after performing sample appearance testing for Example 7 of the present application; Figure 8 Microscope image of the sample after performing sample appearance testing for Example 8 of the present application; Figure 9 Microscope image of the sample after performing sample appearance testing for Example 9 of the present application; Figure 10 Microscope image of the sample after performing sample appearance testing for Example 10 of the present application.

[0103] The ceramic packaging substrates of Examples 11-16 were subjected to performance testing using a copper electroplating solution, and the results of the testing are shown in Table 9 below:

[0104] Table 9 Performance testing results of ceramic packaging substrates of Examples 11-16 using a copper electroplating solution

[0105]

[0106] Figure 11 Microscope image of the sample after performing sample appearance testing for Example 11 of the present application; Figure 12 Microscope image of the sample after performing sample appearance testing for Example 12 of the present application; Figure 13Microscope photograph of the sample after performing the sample appearance test for Example 13 of the present invention; Figure 14 Microscope photograph of the sample after performing the sample appearance test for Example 14 of the present invention; Figure 15 Microscope photograph of the sample after performing the sample appearance test for Example 15 of the present invention; Figure 16 Microscope photograph of the sample after performing the sample appearance test for Example 16 of the present invention.

[0107] The ceramic packaging substrate plating copper solution of Comparative Examples 1-5 was subjected to performance test, and the test results are shown in Table 10 below:

[0108] Table 10 Performance test results of the ceramic packaging substrate plating copper solution of Comparative Examples 1-5

[0109]

[0110] Figure 17 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 1 of the present invention; Figure 18 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 2 of the present invention; Figure 19 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 3 of the present invention; Figure 20 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 4 of the present invention; Figure 21 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 5 of the present invention.

[0111] As can be seen from Table 10, if the ceramic packaging substrate plating copper solution prepared by using sulfuric acid not within the mass concentration range defined in the present invention (Comparative Example 1), the ceramic packaging substrate plating copper solution prepared by using copper sulfate pentahydrate not within the mass concentration range defined in the present invention (Comparative Example 2), the ceramic packaging substrate plating copper solution prepared by using chloride ion not within the mass concentration range defined in the present invention (Comparative Example 3), the ceramic packaging substrate plating copper solution prepared by using a leveling agent not within the type defined in the present invention (Comparative Example 4), and the ceramic packaging substrate plating copper solution prepared by using an accelerator not within the mass concentration range defined in the present invention (Comparative Example 5), the performance test results thereof are all not ideal.

[0112] The ceramic packaging substrate plating copper solution of Comparative Examples 6-10 was subjected to performance test, and the test results are shown in Table 11 below:

[0113] Table 11 Performance test results of the ceramic packaging substrate plating copper solution of Comparative Examples 6-10

[0114]

[0115] Figure 22 Microscope photograph of the sample after performing the sample appearance test for Comparative Example 6 of the present invention;Figure 23 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 7; Figure 24 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 8; Figure 25 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 9; Figure 26 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 10.

[0116] As can be seen from Table 11, the performance test results of the electroplating copper solution for ceramic packaging substrates prepared using an accelerator not within the range of the mass concentration defined in the present application (Comparative Example 6), an inhibitor not within the range of the mass concentration defined in the present application (Comparative Examples 7 and 8), and octylphenol polyoxyethylene and nonylphenol polyoxyethylene not within the range of the mass ratio defined in the present application (Comparative Examples 9 and 10) were not ideal.

[0117] The electroplating copper solution for ceramic packaging substrates of Comparative Examples 11-16 was subjected to performance tests, and the test results are shown in Table 12 below:

[0118] Table 12 Performance test results of the electroplating copper solution for ceramic packaging substrates of Comparative Examples 11-16

[0119]

[0120] Figure 27 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 11; Figure 28 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 12; Figure 29 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 13; Figure 30 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 14; Figure 31 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 15; Figure 32 Microscope photograph of the sample after performing the sample appearance test for Inventive Comparative Example 16.

[0121] As can be seen from Table 12, if the plating copper solution for ceramic packaging substrate is prepared by using the leveler not within the quality concentration range defined in the present application (Comparative Example 11, Comparative Example 12), the performance test results are not ideal. If the plating is performed by using the current density not within the range defined in the present application (in the use method of the plating copper solution for ceramic packaging substrate) (Comparative Example 13, Comparative Example 14), the performance test results are not ideal. If the plating is performed by using the anode type not within the range defined in the present application (in the use method of the plating copper solution for ceramic packaging substrate) (Comparative Example 15, Comparative Example 16), the performance test results are not ideal.

[0122] In summary, the present application provides a plating copper solution for ceramic packaging substrate and a use method thereof. The 3-sulfur-isothiuronium propyl sulfonic acid sodium compound in the plating copper solution can maintain good accelerator function under the condition of large current density plating and oxygen evolution at the anode. The octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether can uniformly disperse the electric power line at large current density in the solution at relatively high temperature (30-50°C). In addition, the accelerator, inhibitor, leveler and other components in the plating copper solution can synergistically cooperate to meet the requirement of 8-12 A / dm 2 2 high current density high speed copper plating.

[0123] The above merely provides a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. Any person skilled in the art can easily think of various equivalent modifications or replacements within the technical range disclosed in the present application, and these modifications or replacements shall be encompassed in the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A plating copper solution for ceramic package substrates, characterized by, The plating solution comprises the following components by mass: 100-200 g / L of sulfuric acid, 100-200 g / L of copper sulfate pentahydrate, 50-80 mg / L of chloride ion, 10-25 mg / L of an accelerator, 200-2000 mg / L of an inhibitor, and 10-20 mg / L of a leveling agent; the accelerator is a 3-thio-isothiuronium propyl sulfonate sodium compound; the leveling agent is 2-mercaptobenzimidazole or 2-mercaptobenzothiazole; the inhibitor is octylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether, and the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether is 1: (0.5-2).

2. The electroplating copper solution for ceramic package substrates according to claim 1, wherein the mass ratio of octylphenol polyoxyethylene ether to nonylphenol polyoxyethylene ether is 1:

1.

3. The electroplating copper solution for ceramic package substrates according to claim 1, wherein The plating solution comprises the following components by mass: 150-200 g / L of sulfuric acid, 100-150 g / L of copper sulfate pentahydrate, 50-80 mg / L of chloride ion, 10-25 mg / L of an accelerator, 200-2000 mg / L of an inhibitor, 10-20 mg / L of a leveling agent, and the balance of deionized water.

4. The electroplating copper solution for ceramic package substrates according to claim 3, wherein The plating solution comprises the following components by mass: 150 g / L of sulfuric acid, 150 g / L of copper sulfate pentahydrate, 70 mg / L of chloride ion, 15 mg / L of an accelerator, 1000 mg / L of an inhibitor, 15 mg / L of a leveling agent, and the balance of deionized water.

5. The use of the electroplating copper solution for ceramic package substrates according to any one of claims 1 to 4, characterized in that, The plating solution comprises the following steps: The plating solution for the ceramic packaging substrate is used to electroplate the product to be plated.

6. The use of a copper electroplating solution for ceramic package substrates according to claim 5, wherein The conditions for the electroplating are: using a direct current power source, the current density of the cathode is 8-12 A / dm 2 .

7. The use of a copper electroplating solution for ceramic package substrates according to claim 6, wherein The temperature of the plating solution for the ceramic packaging substrate is 30-50°C.

8. The use of a copper electroplating solution for ceramic package substrates according to claim 7, wherein The anode of the electroplating is a titanium anode coated with an iridium-tantalum coating, and the cathode of the electroplating is the product to be plated.

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