Low-foam developing additive for developing IC (integrated circuit) carrier plate and developing method of low-foam developing additive

Abstract

The invention discloses a low-foam developing additive for developing an IC (integrated circuit) support plate and a developing method of the low-foam developing additive, and relates to the technical field of IC support plate production. The low-foam developing additive for developing the IC substrate comprises the following components in mass concentration: 1.0-3.0% of an accelerant; 1.0%-3.0% of a wetting agent; 0.5 to 2.0 percent of a protective agent; 1.5%-3.5% of a chelating agent; and 0.2-1.0% of a foam inhibitor. The low-foam developing additive for developing the IC support plate has the advantages of low foam, high efficiency, accurate development, stability, durability, wide compatibility and the like, can be applied to the developing process of the IC support plate with the line width / line spacing of 10 microns, and is clear and complete in developed pattern and low in developing residual rate.

Description

Technical Field

[0001] The present invention relates to the technical field of IC carrier board production, and particularly to a low-foaming developing additive for IC carrier board development and a developing method thereof. Background Art

[0002] With the vigorous development of modern electronic technology, integrated circuit (IC) technology is accelerating its evolution towards high integration, small size, and high performance. As an essential component of integrated circuits, IC carrier boards not only provide physical support for chips, achieve electrical interconnection, but also effectively protect chips from damage by the external environment. Nowadays, as the chip integration continues to increase and the manufacturing process becomes increasingly complex and precise, extremely stringent requirements are put forward for indicators such as the manufacturing accuracy and line resolution of IC carrier boards.

[0003] In the IC carrier board manufacturing process, the developing process is a key link in the lithography process. Its core function is to selectively remove the photoresist in the exposed area through chemical dissolution, thereby achieving high-fidelity circuit pattern transfer. However, the long-existing bubble defect problem in this process severely restricts the process yield. The current developing additives are prone to induce micro-bubble nucleation during the dynamic developing process. These bubbles adsorb on the substrate surface to form a local barrier layer, resulting in hindrance to the interfacial reaction between the developing solution and the photoresist, and causing defects such as uneven development, pattern distortion, and critical dimension deviation. According to industry data statistics, in the production of high-order carrier boards, bubble defects can cause a yield loss of 10 - 20%, significantly increasing the unit production cost. In addition, the accumulation of foam will also cause frequent equipment shutdown for maintenance, reducing the production capacity utilization rate. Therefore, developing new additives with low-foaming characteristics and capable of optimizing the developing performance has important engineering application value for improving the process yield and reducing the overall cost.

[0004] Currently, there are some technical solutions introduced for developing additives. For example, Patent CN113093481A discloses a developing additive, its preparation method and application. The components of this developing additive include: modified cellulose salt, water-soluble derivative of vitamin E, bentonite, and solvent, which can prevent the further polymerization of unexposed substances, isolate and encapsulate the unexposed polymerized substances, and discharge them through the overflow of the tank body, avoiding adhesion to equipment such as the tank wall, rollers, pipelines, and board surface, enabling the tank body to be clean, improving the product yield, and reducing the production cost. Patent CN113504715B discloses a developing additive for printed circuit boards. This additive includes: a developing accelerator with a mass fraction of 3 - 15%; a wetting agent with a mass concentration of 100 - 4000 ppm; a copper surface stabilizer with a mass concentration of 50 - 2000 ppm. This developing additive can increase the production speed by 20 - 40%, has stable quality, significantly improves quality problems such as film debris re-adhesion, notch, and incomplete development, has low use cost, is environmentally friendly and pollution-free, is easy to treat waste liquid, and is non-toxic and harmless.

[0005] Existing developing additives can basically meet the requirements of conventional PCB production processes. However, with the development of IC substrate manufacturing towards higher precision and higher integration, the developing process has become increasingly complex. There are many deficiencies in the application of existing products in the low-foam field, which seriously restricts the further development of IC substrate manufacturing processes. First of all, ordinary additives are difficult to quickly destroy the stability of bubbles, resulting in a large accumulation of bubbles and affecting the developing uniformity. For example, due to the insufficient defoaming ability of the developing additive, the developing defect rate of the product may soar from the original 5% to 15%. Secondly, ordinary additives may have a negative impact on the developing solution for IC substrates, such as reducing the developing rate and destroying the stability of the developing solution. This not only reduces production efficiency but also may cause potential damage to other properties of the IC substrate due to long-term development. Moreover, it is easy to cause secondary pollution and residue problems. If these residual substances cannot be completely removed in the subsequent cleaning process, they will have an adverse impact on the subsequent processes of the IC substrate, such as electroplating and soldering, resulting in poor soldering and increasing the defective rate of the product. Therefore, it is very meaningful to develop a low-foam developing additive for IC substrate development. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention provides a low-foam developing additive for IC substrate development, its preparation method and developing method, which are applied to the developing process of IC substrates. The low-foam developing additive contains effective components such as a promoter, a wetting agent, a protective agent, a chelating agent, and an antifoaming agent. Among them, the promoter is a substance containing two hydrophilic groups and two hydrophobic tail chains, and the hydrophilic groups are connected by chemical bonds, having a lower critical micelle concentration and stronger performance of reducing the surface tension of the target solution, playing a role in promoting the ionization of the developing solution and accelerating the developing speed; the wetting agent can accelerate the penetration of the developing additive components into the pores of the dry film and improve the penetration efficiency; the protective agent can prevent the developing solution from being oxidized and extend the service life of the developing solution; the chelating agent can chelate metal ions in the developing tank to prevent the effective components in the developing solution from being contaminated; the antifoaming agent can prevent the formation of bubbles or delay the generation speed of bubbles by reducing the liquid surface tension and destroying the stability of the foam.

[0007] First of all, the present invention provides a low-foam developing additive for IC substrate development, comprising the following components in mass concentration: Promoter 1.0 - 3.0%; Wetting agent 1.0 - 3.0%; Protective agent 0.5 - 2.0%; Chelating agent 1.5 - 3.5%; Antifoaming agent 0.2 - 1.0%; The promoter has the structure of the following formula (1): (1); In formula (1), the degree of polymerization n = 2, 3, 4; The wetting agent is selected from one or a mixture of more than one of tetrafluoromethylurea hexafluorophosphate (CAS No.: 678-41-1), tris(pentafluorophenyl) phosphate (CAS No.: 3806-34-6), bis(2-(perfluorooctyl)ethyl) phosphate (CAS No.: 2795-39-3); The protective agent is selected from one or a mixture of more than one of bisphenol A diallyl ether (CAS No.: 3739-67-1), bisphenol A bis(2,3-dihydroxypropyl) ether (CAS No.: 5581-32-8), bisphenol A diglycidyl ether (CAS No.: 1675-54-3); The chelating agent is selected from one or a mixture of more than one of 4-mercaptobenzoic acid (CAS No.: 1074-36-8), 4-mercaptobutyric acid (CAS No.: 13095-73-3), 2-mercaptobenzimidazole carboxylic acid (CAS No.: 58089-25-1); The defoaming agent is selected from one or a mixture of more than one of N-phenylbenzylhydroxylamine (CAS No.: 621-07-8), 2,4-dichlorobenzylhydroxylamine (CAS No.: 3299-92-1), N-benzyl-N-hydroxyacetamide (CAS No.: 495-18-1).

[0008] The preparation method of the accelerator in the present invention is as follows: First, 2,5-di-tert-amylhydroquinone, ethylene oxide, acetonitrile, triethylamine and potassium hydroxide are placed in a high-pressure reaction kettle. After the air in the reaction kettle is discharged, the temperature is raised to 80 ± 2 °C and reacted for 45 - 50 h, and then cooled to room temperature to collect the crude product; then the crude product is subjected to rotary evaporation, dichloromethane solvent extraction, and drying treatment to obtain the accelerator. By adjusting the molar ratio of 2,5-di-tert-amylhydroquinone and ethylene oxide, accelerators with different degrees of polymerization n can be obtained. When the ratio of the two is 1:4, n = 2; when the ratio of the two is 1:6, n = 3; when the ratio of the two is 1:8, n = 4.

[0009] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-di-tert-amylhydroquinone (CAS No.: 79-74-3) and 1.6 mol of ethylene oxide (CAS No.: 75-21-8) are added into a 5 L high-pressure reactor, 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80 °C and reacted for 48 h, then the temperature is lowered to room temperature to collect the crude product; then the crude product is subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying treatment to obtain the accelerator with a polymerization degree n of 2 as shown in the following formula (2); (2).

[0010] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-di-tert-amylhydroquinone (CAS No.: 79-74-3) and 2.4 mol of ethylene oxide (CAS No.: 75-21-8) are added into a 5 L high-pressure reactor, 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80 °C and reacted for 48 h, then the temperature is lowered to room temperature to collect the crude product; then the crude product is subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying treatment to obtain the accelerator with a polymerization degree n of 3 as shown in the following formula (3); (3).

[0011] In some specific embodiments, the preparation method of the accelerator is as follows: 0.4 mol of 2,5-di-tert-amylhydroquinone (CAS No.: 79-74-3) and 3.2 mol of ethylene oxide (CAS No.: 75-21-8) are added into a 5 L high-pressure reactor, 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, the temperature is raised to 80 °C and reacted for 48 h, then the temperature is lowered to room temperature to collect the crude product; then the crude product is subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying treatment to obtain the accelerator with a polymerization degree n of 4 as shown in the following formula (4); (4).

[0012] Preferably, the low-foaming developing additive for IC substrate developing is composed of components with the following mass concentrations: Accelerator: 1.0 - 3.0%; Wetting agent: 1.0 - 3.0%; Protective agent: 0.5 - 2.0%; Chelating agent: 1.5 - 3.5%; Defoaming agent: 0.2 - 1.0%; The balance is water.

[0013] The preparation method of the above low-foaming developing additive for IC substrate developing is as follows: Weigh the accelerator, wetting agent, protective agent, chelating agent, and defoaming agent according to the required mass concentrations, add them to water, and mix evenly at room temperature. The obtained liquid medicine is sealed and stored for later use.

[0014] The present invention also provides a developing solution containing the above low-foaming developing additive for IC substrate developing (hereinafter referred to as low-foaming developing additive).

[0015] Preferably, the developing solution contains 0.3 - 0.6% by mass concentration of the above low-foaming developing additive.

[0016] The present invention also provides a developing method for the developing process in IC substrate production; it sequentially includes the following steps of developing stage 1 and developing stage 2: Developing stage 1: Spraying the IC substrate with the developing solution of developing stage 1; the developing solution of developing stage 1 is composed of 1.0 - 1.5% by mass concentration of sodium carbonate, 0.4 - 0.6% of the above low-foaming developing additive, and the balance of water. The spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s; Developing stage 2: Spraying the IC substrate processed in developing stage 1 with the developing solution of developing stage 2; the developing solution of developing stage 2 is composed of 0.5 - 1.0% by mass concentration of sodium carbonate, 0.3 - 0.4% of the above low-foaming developing additive, and the balance of water. The spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s.

[0017] The function of developing stage 1 is to quickly dissolve the unexposed dry film, so that the circuit pattern is initially shown on the circuit board. The function of developing stage 2 is to remove the remaining undeveloped substances, make the circuit pattern clearer and more complete, improve the quality and accuracy of developing, and ensure that the circuit pattern on the circuit board meets the design requirements.

[0018] Preferably, the above-described developing method further includes a pre-soaking section before the first developing section: immersing the exposed IC substrate in the pre-soaking section chemical solution for 15 ± 2 s; the pre-soaking section chemical solution consists of sodium carbonate with a mass concentration of 0.4 - 0.6% and the balance of water. The function of the pre-soaking section is to loosen the unexposed dry film with sodium carbonate, which helps to quickly remove the dry film in the first developing section and the second developing section.

[0019] In some specific embodiments, the developing method of the present invention sequentially includes the following steps of a pre-soaking section, a first developing section, and a second developing section: Pre-soaking section: Immerse the exposed IC substrate in the pre-soaking section chemical solution for 15 ± 2 s; the pre-soaking section chemical solution consists of sodium carbonate with a mass concentration of 0.5% and the balance of water; First developing section: Spray the IC substrate with the first developing section developer; the first developing section developer consists of sodium carbonate with a mass concentration of 1.2%, 0.6% of the above-mentioned low-foaming developing additive, and the balance of water, and the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s; Second developing section: Spray the IC substrate processed in the first developing section with the second developing section developer; the second developing section developer consists of sodium carbonate with a mass concentration of 0.6%, 0.3% of the above-mentioned low-foaming developing additive, and the balance of water, and the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s.

[0020] The low-foaming developing additive for IC substrate developing of the present invention has the advantages of low foaming and high efficiency, precise developing, stable and durable, and wide compatibility. It can be applied to the developing process of IC substrates with a line width / line pitch of 10 μm. After developing, the pattern is clear and complete, the developing residue rate is low, which is beneficial to the high-precision forming of IC substrates. The product has good stability and excellent compatibility with dry film and metal surface, can reduce the defective rate of IC substrate developing, and improve the manufacturing efficiency. Description of the Drawings

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0022] Figure 1 It is the developed pattern observed by an optical microscope after developing in Example 1; Figure 2 It is the developed pattern observed by an optical microscope after developing in Example 4; Figure 3 It is the developed pattern observed by an optical microscope after developing in Comparative Example 12; Figure 4 The developed pattern observed by optical microscope after development for Comparative Example 13. Detailed implementation manners

[0023] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] It should be noted that the contents or concentrations described in the following examples / comparative examples are all mass concentrations.

[0025] The preparation method of the accelerator in Example 1, Example 4, and Example 5 is as follows: Add 0.4 mol of 2,5 - di - tert - amylhydroquinone (CAS No.: 79 - 74 - 3) and 1.6 mol of ethylene oxide (CAS No.: 75 - 21 - 8) into a 5 - L high - pressure reactor, add 800 mL of acetonitrile (CAS No.: 75 - 05 - 8), 0.024 mol of triethylamine (CAS No.: 121 - 44 - 8), and 0.012 mol of potassium hydroxide (CAS No.: 1310 - 58 - 3). Evacuate the air in the reactor, raise the temperature to 80 °C and react for 48 h, then lower the temperature to room temperature to collect the crude product; then perform rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75 - 09 - 2), and drying treatment on the crude product to obtain the accelerator of this example with a polymerization degree n of 2.

[0026] The preparation method of the accelerator in Example 2 is as follows: Add 0.4 mol of 2,5 - di - tert - amylhydroquinone (CAS No.: 79 - 74 - 3) and 2.4 mol of ethylene oxide (CAS No.: 75 - 21 - 8) into a 5 - L high - pressure reactor, add 800 mL of acetonitrile (CAS No.: 75 - 05 - 8), 0.024 mol of triethylamine (CAS No.: 121 - 44 - 8), and 0.012 mol of potassium hydroxide (CAS No.: 1310 - 58 - 3). Evacuate the air in the reactor, raise the temperature to 80 °C and react for 48 h, then lower the temperature to room temperature to collect the crude product; then perform rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75 - 09 - 2), and drying treatment on the crude product to obtain the accelerator with a polymerization degree n of 3.

[0027] The preparation method of the accelerator in Example 3 is as follows: 0.4 mol of 2,5-di-tert-amylhydroquinone (CAS No.: 79-74-3) and 3.2 mol of ethylene oxide (CAS No.: 75-21-8) are added into a 5 L high-pressure reactor, and 800 mL of acetonitrile (CAS No.: 75-05-8), 0.024 mol of triethylamine (CAS No.: 121-44-8) and 0.012 mol of potassium hydroxide (CAS No.: 1310-58-3) are added. The air in the reactor is discharged, and after reacting at 80 °C for 48 h, the temperature is lowered to room temperature to collect the crude product; then the crude product is subjected to rotary evaporation, solvent extraction with dichloromethane (CAS No.: 75-09-2), and drying treatment to obtain an accelerator with a polymerization degree n of 4.

[0028] The preparation methods of the developing additives in Examples 1-5 below are as follows: According to the formulations of Examples 1-5, the accelerator, wetting agent, protective agent, chelating agent, antifoaming agent and the remaining amount of water are weighed in sequence and added into a reactor, and stirred and mixed at room temperature for 30 minutes to obtain the low-foaming developing additives corresponding to the examples. The obtained low-foaming developing additive solutions are sealed and stored for standby.

[0029] Example 1: The content of the accelerator is 2.0%, specifically ; The content of the wetting agent is 2.0%, specifically tetramethylfluorourea hexafluorophosphate; The content of the protective agent is 1.0%, specifically bisphenol A diallyl ether; The content of the chelating agent is 2.0%, specifically 4-mercaptobenzoic acid; The content of the antifoaming agent is 0.5%, specifically N-phenylbenzylhydroxylamine; The remaining amount is water.

[0030] Example 2: The content of the accelerator is 2.0%, specifically ; The content of the wetting agent is 2.0%, specifically tris(pentafluorophenyl) phosphate; The content of the protective agent is 1.0%, specifically bisphenol A bis(2,3-dihydroxypropyl) ether; The content of the chelating agent is 2.0%, specifically 4-mercaptobutyric acid; The content of the antifoaming agent is 0.5%, specifically 2,4-dichlorobenzylhydroxylamine; The remaining amount is water.

[0031] Example 3: The content of the accelerator is 2.0%, specifically ; The wetting agent content is 2.0%, specifically bis(2-(perfluorooctyl)ethyl) phosphate; The protective agent content is 1.0%, specifically bisphenol A diglycidyl ether; The chelating agent content is 2.0%, specifically 2-mercaptobenzimidazole carboxylic acid; The defoaming agent content is 0.5%, specifically N-benzyl-N-hydroxyacetamide; The balance is water.

[0032] Example 4: The accelerator content is 1.0%, specifically ; The wetting agent content is 1.0%, specifically tetramethylfluorourea hexafluorophosphate; The protective agent content is 0.5%, specifically bisphenol A diallyl ether; The chelating agent content is 1.5%, specifically 4-mercaptobenzoic acid; The defoaming agent content is 0.2%, specifically N-phenylbenzylhydroxylamine; The balance is water.

[0033] Example 5: The accelerator content is 3.0%, specifically ; The wetting agent content is 3.0%, specifically tetramethylfluorourea hexafluorophosphate; The protective agent content is 2.0%, specifically bisphenol A diallyl ether; The chelating agent content is 3.5%, specifically 4-mercaptobenzoic acid; The defoaming agent content is 1.0%, specifically N-phenylbenzylhydroxylamine; The balance is water.

[0034] Based on Example 1, develop the developer for Comparative Examples 1-12.

[0035] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is only that the accelerator is not included in the components.

[0036] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is only that the wetting agent is not included in the components.

[0037] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is only that the protective agent is not included in the components.

[0038] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is only that the chelating agent is not included in the components.

[0039] Comparative Example 5 Comparative Example 5 is different from Example 1 only in that the defoamer is not included in the components.

[0040] Comparative Example 6 Comparative Example 6 is different from Example 1 only in that the concentration of the accelerator in the components is 6.0%.

[0041] Comparative Example 7 Comparative Example 7 is different from Example 1 only in that the concentration of the wetting agent in the components is 6.0%.

[0042] Comparative Example 8 Comparative Example 8 is different from Example 1 only in that the concentration of the protective agent in the components is 4.0%.

[0043] Comparative Example 9 Comparative Example 9 is different from Example 1 only in that the concentration of the chelating agent in the components is 7.0%.

[0044] Comparative Example 10 Comparative Example 10 is different from Example 1 only in that the concentration of the defoamer in the components is 2.0%.

[0045] Comparative Example 11 Comparative Example 11 is different from Example 1 only in that the degree of polymerization n of the accelerator is 1, as shown in the following formula (5); that is, in the preparation method of the accelerator in Comparative Example 11, 0.4 mol of 2,5-di-tert-amylhydroquinone and 0.8 mol of ethylene oxide are used, and the molar ratio of the two is 1:2; (5).

[0046] Comparative Example 12 Comparative Example 12 is different from Example 1 only in that the degree of polymerization n of the accelerator is 5, as shown in the following formula (6); that is, in the preparation method of the accelerator in Comparative Example 11, 0.4 mol of 2,5-di-tert-amylhydroquinone and 4.0 mol of ethylene oxide are used, and the molar ratio of the two is 1:10; (6).

[0047] Comparative Example 13 Comparative Example 13 is a developing additive disclosed in the prior art CN113504715B. Specifically, its components include: 4% diethylenetriaminepentaacetic acid, 600 ppm of ethylene glycol, 400 ppm of oxalic acid, and the balance of water.

[0048] The following foam performance, developing performance, stability performance, and compatibility performance of the above examples / comparative examples of developing additives were detected. The specific detection methods are as follows: 1) Foam performance: Take the developing additives of the examples / comparative examples, add tap water to prepare a solution with a concentration of 0.6%, and use an RM-2 digital-display Ross foam meter for testing. The test temperature is 25 °C. During the test process, avoid ventilation or vibration affecting the foam stability, and record the initial foam height (unit: mm, denoted as H0) and the time when the foam dissipates to half of its height (t 1 / 2 ), and perform at least 3 parallel tests on each sample, and take the average value; 2) Developing performance: Use the developing additives of the examples / comparative examples for the development of an IC carrier board with a line width / line pitch of 10 μm according to the following developing process flow; observe whether the pattern can be developed clearly, and use a SU1510 type scanning electron microscope to test the remaining ratio of the dry film on the surface of the circuit board after development, that is, the developing residue rate, and the developing residue rate should be ≤ 0.5%; The developing process flow is: degreasing → water washing → drying → film laminating → exposure → developing → water washing → etching → water washing → film stripping → water washing → drying; among them, the developing additives of the examples / comparative examples are used in the developing process, which is divided into three treatment sections: pre-soaking section → developing section 1 → developing section 2; The process parameters of the pre-soaking section are: the solution composition in the pre-soaking tank is 0.5% sodium carbonate, and the balance is water; this section is an immersion type, the pre-soaking temperature is 25 ± 1 °C, the length of the pre-soaking section is 0.5 m, and the linear speed is 2.0 ± 0.2 m / min; The process parameters of the developing section 1 are: this section is a spray type, and the composition of the developing solution in the developing tank of the developing section 1 is 1.2% sodium carbonate, 0.6% developing additive prepared from the examples / comparative examples, and the balance is tap water; the developing temperature is 25 ± 1 °C, and the length of the developing section 1 is 1.0 m; the linear speed is 2.0 ± 0.2 m / min, and the pressure is 1.5 ± 0.5 kg / cm 2 ; The process parameters of the developing section 2 are: this section is a spray type, and the composition of the developing solution in the developing tank of the developing section 2 is 0.6% sodium carbonate, 0.3% developing additive prepared from the examples / comparative examples, and the balance is tap water; the developing temperature is 25 ± 1 °C, and the length of the developing section is 1.0 m; the linear speed is 2.0 ± 0.2 m / min, and the pressure is 1.0 ± 0.5 kg / cm 2 ; 3) Stability performance: First is storage stability, that is, the developing additive is stored at 40 °C for 7 days, and observe the change in the surface tension of the solution on the first day and the seventh day. The test method for surface tension is the capillary rise method. Specifically, insert a clean capillary vertically into the developing additive of the examples / comparative examples. Due to the action of surface tension, the solution will rise to a certain height in the capillary; according to parameters such as the capillary radius, solution density, gravitational acceleration, and the height of the solution rising in the capillary, the surface tension of the solution can be calculated using relevant formulas. The calculation formula is where γ is the surface tension; r is the capillary radius; h is the height of the solution rising in the capillary; ρ is the density of the solution; g is the acceleration due to gravity; θ is the contact angle; 4) Compatibility performance: Immerse the developing additives of the examples / comparative examples in the IC carrier board material and observe whether the dry film swells and whether the metal surface corrodes. If there are no such phenomena, the test result is excellent; if such phenomena occur, the test result is poor.

[0049] The performance test results of Examples 1-5 and Comparative Examples 1-13 are shown in Table 1: Table 1 Performance test results

[0050] The developed pattern observed by optical microscope after developing Example 1 is as Figure 1 shown; the developed pattern observed by optical microscope after developing Example 4 is as Figure 2 shown; the developed pattern observed by optical microscope after developing Comparative Example 12 is as Figure 3 shown; the developed pattern observed by optical microscope after developing Comparative Example 13 is as Figure 4 shown.

[0051] It can be seen from the experimental data of Examples 1-5 in Table 1 that the foam height of the low-foam developing additive for IC carrier board development of the present invention is 2.5 - 2.9 mm, and the time for half of the foam to disappear is 2.0 - 2.2 s; the developing residue rate of the 10-μm line width / line pitch circuit board is 0.02 - 0.06%; the surface tension of the product remains unchanged on the first day and the seventh day, and the stability performance is excellent; when the circuit board surface is immersed in the developing additive of the present invention, the dry film does not swell and the metal surface has no corrosion, and the compatibility performance is excellent. It shows that the low-foam developing additive for IC carrier board development of the present invention has the advantages of low foam, rapid defoaming, thorough development, stable and durable, and wide compatibility, and can be applied to the developing process of IC carrier boards with a 10-μm line width / line pitch. After development, the pattern is clear and complete, the developing residue rate is low, which is beneficial to the high-precision forming of IC carrier boards, the stability performance of the product is good, and the compatibility performance with the dry film and the metal surface is excellent, which can reduce the defective rate of IC carrier board development and improve the manufacturing efficiency.

[0052] The differences between Comparative Examples 1-5 and Example 1 are that they respectively lack a single component of accelerator, wetting agent, protective agent, chelating agent, and defoaming agent. The test results show that after the absence of the accelerator and defoaming agent, the foam height, development residue rate, and product surface tension are greatly affected, indicating that the accelerator and defoaming agent components contribute to accelerating development, fine development, and providing a low surface tension; after the absence of the wetting agent, protective agent, and chelating agent, the foam height, development residue rate, and product surface tension of the development additive all show a slight decrease, and the product compatibility performance deteriorates, indicating that these three types of components all play a certain role in the development additive. Therefore, the excellent performance of the low-foam development additive for IC substrate development in the present invention is the result of the interaction of each component, and the absence of any one component will affect the product performance.

[0053] The differences between Comparative Examples 6-10 and Example 1 are that the accelerator, wetting agent, protective agent, chelating agent, and defoaming agent are respectively higher than the upper concentration limit of the present invention. The test results show that compared with Examples 1-5, too high concentrations of the accelerator, wetting agent, protective agent, chelating agent, and defoaming agent will not affect the development performance, but too high concentrations will increase the cost of the chemical solution. Therefore, the concentrations of each component of the development additive in the present invention should not be too high, and a stable development effect of the chemical solution can be ensured within the concentration range defined in the present invention.

[0054] The difference between Comparative Example 11 and Example 1 is only that the polymerization degree n of the accelerator is 1. From the test results of Example 1 and Comparative Example 11, it can be seen that the foam performance, development residue rate, and compatibility performance of Comparative Example 11 are basically the same as those of Example 1, but the stability performance of the product is relatively poor, and the product surface tension is also slightly higher, and it is easy to cause poor development when used for too long.

[0055] The difference between Comparative Example 12 and Example 1 is only that the polymerization degree n of the accelerator is 5. From the test results of Example 1 and Comparative Example 12, it can be seen that the foam performance, development residue rate, and compatibility performance of Comparative Example 12 are poor and it is difficult to meet the requirements of IC substrate development.

[0056] Comparative Example 13 uses a development additive of the prior art. The comparison of the test results with those of Example 1 shows that the low-foam development additive for IC substrate development in the present invention has a lower foam height, faster defoaming time, lower development residue rate, lower surface tension and stability performance, and better compatibility performance, and can be applied to the development process of IC substrates.

[0057] In summary, the present invention provides a low-foam developing additive for IC substrate development. This product has the advantages of low foam and high efficiency, precise development, stable and durable performance, and wide compatibility. It can be applied to the development process of IC substrates with a line width / line pitch of 10 μm. After development, the pattern is clear and complete, and the development residue rate is low, which is beneficial to the high-precision forming of IC substrates. The product has good stability and excellent compatibility with dry film and metal surface, can reduce the defective rate of IC substrate development, and improve the manufacturing efficiency.

[0058] As described above, the above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A low-foaming developing additive for IC substrates, characterized in that, Comprising components with the following mass concentrations: Accelerator: 1.0 - 3.0%; Wetting agent: 1.0 - 3.0%; Protectant: 0.5 - 2.0%; Chelating agent: 1.5 - 3.5%; Defoaming agent: 0.2 - 1.0%; The accelerator has the structure of the following formula (1): （1）； In formula (1), the degree of polymerization n = 2, 3, 4; The wetting agent is selected from one or a mixture of more of tetra - methylfluorourea hexafluorophosphate, tris(pentafluorophenyl) phosphate, bis(2 - (perfluorooctyl)ethyl) phosphate; The protectant is selected from one or a mixture of more of bisphenol A diallyl ether, bisphenol A bis(2,3 - dihydroxypropyl) ether, bisphenol A diglycidyl ether; The chelating agent is selected from one or a mixture of more of 4 - mercaptobenzoic acid, 4 - mercaptobutyric acid, 2 - mercaptobenzimidazole carboxylic acid; The defoaming agent is selected from one or a mixture of more of N - phenylbenzylhydroxylamine, 2,4 - dichlorobenzylhydroxylamine, N - benzyl - N - hydroxyacetamide.

2. The low-foaming developing additive for IC substrate developing according to claim 1, wherein, The preparation method of the accelerator is as follows: First, put 2,5 - di - tert - amylhydroquinone, ethylene oxide, acetonitrile, triethylamine and potassium hydroxide into a high - pressure reaction kettle. After discharging the air in the reaction kettle, heat it to 80 ± 2 °C and react for 45 - 50 h. Then cool it to room temperature and collect the crude product. Then perform rotary evaporation, dichloromethane solvent extraction and drying on the crude product to obtain the accelerator. By adjusting the molar ratio of 2,5 - di - tert - amylhydroquinone and ethylene oxide, accelerators with different degrees of polymerization n can be obtained. When the ratio of the two is 1:4, n = 2; when the ratio is 1:6, n = 3; when the ratio is 1:8, n = 4.

3. The low-foam developing additive for IC substrate development according to claim 1, wherein Composed of components with the following mass concentrations: Accelerator: 1.0 - 3.0%; Wetting agent: 1.0 - 3.0%; Protectant: 0.5 - 2.0%; Chelating agent: 1.5 - 3.5%; Defoaming agent: 0.2 - 1.0%; The balance is water.

4. The preparation method of the low-foaming developing additive for IC substrate development according to any one of claims 1-3, characterized in that Weigh the accelerator, wetting agent, protectant, chelating agent and defoaming agent according to the required mass concentration, add them to water, and mix evenly at room temperature to obtain a low - foam developing additive for IC substrate development.

5. A developer, characterized in that, Containing the low - foam developing additive for IC substrate development as described in any one of claims 1 - 3.

6. The developer according to claim 5, characterized in that, Containing the low - foam developing additive for IC substrate development with a mass concentration of 0.3 - 0.6%.

7. The developer according to claim 5 or 6, characterized in that, Applied to the development of IC substrates with a line width / line pitch of 10 μm.

8. A developing method for the developing process in the production of IC substrates, characterized in that, Sequentially including the following developing step 1 and developing step 2: Development stage 1: Spray the IC carrier board with the developer solution for development stage 1; the developer solution for development stage 1 is composed of sodium carbonate with a mass concentration of 1.0 - 1.5%, the low-foaming developer additive for IC carrier board development as described in any one of claims 1 - 3 with a mass concentration of 0.4 - 0.6%, and the balance being water, the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s; Developing in two stages: Spraying the developing solution in two stages on the IC carrier board after the first-stage treatment; the developing solution for the second stage of developing consists of sodium carbonate with a mass concentration of 0.5 - 1.0%, the low-foaming developing additive for IC carrier board development described in any one of claims 1 - 3 with a mass concentration of 0.3 - 0.4%, and the balance being water, the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s.

9. The developing method according to claim 8, wherein Before developing step 1, there is also a pre - dipping section: Immerse the exposed IC substrate in the pre - dipping section solution for 15 ± 2 s; The pre - dipping section solution consists of sodium carbonate with a mass concentration of 0.4 - 0.6% and the balance water.

10. A developing method, characterized in that, Sequentially including the following pre - dipping section, developing step 1 and developing step 2: Pre - dipping section: Immerse the exposed IC substrate in the pre - dipping section solution for 15 ± 2 s; The pre - dipping section solution consists of sodium carbonate with a mass concentration of 0.5% and the balance water; Development stage 1: Spray the IC carrier board with the developer solution for development stage 1; the developer solution for development stage 1 consists of sodium carbonate with a mass concentration of 1.2%, the low-foaming developer additive for IC carrier board development described in any one of claims 1-3 with a concentration of 0.6%, and the balance of water, and the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s; Developing in two stages: Spraying the developing solution for two-stage development on the IC carrier board after the one-stage development treatment; the developing solution for two-stage development consists of sodium carbonate with a mass concentration of 0.6%, the low-foaming developing additive for IC carrier board development described in any one of claims 1-3 with a mass concentration of 0.3%, and the balance being water, the spraying pressure is 1.5 ± 0.5 kg / cm 2 , and the spraying time is 30 ± 5 s.

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