Gelatin-based polymer molecular brushes, surface treatment solutions and their applications

Abstract

This invention relates to a gelatin-based polymer molecular brush, a surface treatment liquid, and its application in semiconductor devices. The gelatin-based polymer molecular brush has a structure as shown in structural formula (I) or (II) or a product of oxidation, coordination, and crosslinking of its catechol groups. The specific steps for processing the surface treatment liquid in a semiconductor device include: contacting the surface treatment liquid with the surface of a first material to form a thin film, and then bonding it to a second material; wherein the contact method is spraying or immersion, and the first and second materials are respectively selected from inorganic materials and / or resin materials. This invention provides a gelatin-based polymer molecular brush that can be used as the main component of a surface treatment liquid for bonding materials, ensuring peel strength between materials without the need for browning treatment, improving adhesion and heat resistance, and enabling its application in semiconductor devices, especially in the manufacture of multilayer PCBs.

Description

Technical Field

[0001] This invention relates to the field of surface treatment technology, and in particular to a gelatin-based polymer molecular brush, a surface treatment liquid, and their application in semiconductor device processing. Background Technology

[0002] With the development of technology, the requirements for high-speed / high-frequency signal transmission performance of multilayer PCBs (printed circuit boards) are constantly increasing. HVLP copper foil, with its extremely low surface roughness and contour structure, can effectively reduce loss and attenuation in high-speed signal transmission and has excellent circuit etching properties, so it is widely used in the field of high-frequency and high-speed copper-clad laminates.

[0003] However, the smooth surface of HVLP copper foil leads to insufficient interlayer bonding, typically requiring a browning process to increase the contact area. But the browning solution used in this process causes environmental pollution and ecological damage. With increasing environmental awareness, developing green and environmentally friendly adhesives or surface treatment solutions has become an important issue. These solutions can not only replace mechanical interlocking through chemical action but also meet environmental requirements and reduce wastewater treatment costs.

[0004] Gelatin, a natural polymer derived from collagen, possesses various functional groups, such as amino, hydroxyl, amide, and carboxyl groups. It has a wide molecular weight distribution, is soluble in hot water, abundant in source, inexpensive, non-toxic, and easy to process, making it a promising candidate for the adhesives field. In the field of polymer science, advanced chemical synthesis techniques can create polymer molecular brushes at the molecular scale, that is, linking polymer molecules to the polymer backbone to form polymer systems with unique structures. This technology provides new insights for improving gelatin materials.

[0005] Gelatin has wide applications in food, pharmaceuticals, cosmetics, and biomaterials, and is particularly favored in the biomedical field due to its biocompatibility and biodegradability. However, traditional gelatin materials have limitations in terms of mechanical properties and functionalization, making it difficult to meet certain application requirements. Therefore, developing a gelatin-based green and environmentally friendly adhesive or surface treatment liquid that combines the application requirements of HVLP copper foil or ordinary copper foil with the properties of gelatin is not only of significant economic importance, but also provides a new solution to address environmental issues in PCB manufacturing. Summary of the Invention

[0006] In the prior art, traditional gelatin materials have certain limitations in terms of mechanical properties and functionalization, making it difficult to meet some application requirements. Therefore, the present invention provides a gelatin-based polymer molecular brush, a surface treatment liquid, and a semiconductor device to solve the above problems.

[0007] To achieve the above objectives, in a first aspect, the present invention provides a gelatin-based polymer molecular brush having a structure as shown in structural formula (I) or (II):

[0008] Formula (I) or Formula (II);

[0009] Where n represents the number of methylene groups, which is an integer from 0 to 12.

[0010] In one implementation, the gelatin-based polymer molecular brush is a product having a structure as shown in structural formula (I) or (II) and its catechol groups after oxidation, coordination, and crosslinking.

[0011] In one implementation, the method for preparing the gelatin-based polymer molecular brush includes the following steps: In a solvent, compound A having structural formula (III) and compound B having general formula (IV) or compound C having general formula (V) are polymerized by heating.

[0012] Equation (III)

[0013] Formula (IV) or Formula (V);

[0014] Where n represents the number of methylene groups, which is an integer from 0 to 12.

[0015] In one implementation, the solvent does not react with compounds A, B, and C, and the solvent includes any one of hydrocarbon solvents, alcohol solvents, amide solvents, ketone solvents, ether solvents, ester solvents, acetonitrile, and dimethyl sulfoxide.

[0016] In one implementation, compound B comprises any one of 3,4-dihydroxybenzaldehyde, 3,4-dihydroxyphenylacetaldehyde, and 3-(3,4-dihydroxyphenyl)propanal.

[0017] In one implementation, compound C comprises any one of 3,4-dihydroxybenzoic acid, 3,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylpropionic acid, 4-(3,4-dihydroxyphenyl)butyric acid, and 5-(3,4-dihydroxyphenyl)valerate.

[0018] In a second aspect, the present invention also provides a surface treatment liquid comprising an organic solvent and / or water, and the aforementioned gelatin-based polymer molecular brush.

[0019] In one implementation, the organic solvent comprises any one of methanol, ethanol, 1-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, diethylene glycol, glycerol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol methyl ether, ethylene glycol monobutyl ether, N-methylpyrrolidone, dimethyl sulfoxide, benzene, toluene, xylene, n-hexane, cyclohexane, dichloromethane, chloroform, dichlorobenzene, acetone, and butanone.

[0020] Thirdly, the present invention also provides an application of a surface treatment liquid in semiconductor device processing.

[0021] In one implementation, the surface treatment liquid is processed in a semiconductor device, which includes the following specific steps: contacting the surface treatment liquid with the surface of a first material to form a thin film, and then bonding it with a second material; wherein the contact method is spraying or immersion, and the first material and the second material are respectively selected from inorganic materials and / or resin materials.

[0022] Beneficial effects: The gelatin-based polymer molecular brush provided by this invention improves the mechanical strength of gelatin-based materials by introducing a specific chemical structure, making it more suitable for applications requiring high-strength materials. The gelatin-based polymer molecular brush can be used as the main component of surface treatment liquids to bond materials, ensuring peel strength between materials and improving bonding force without the need for browning treatment. It also has good heat resistance and can be used in the processing of semiconductor devices, especially in the manufacture of multilayer PCBs, providing semiconductor devices with better performance and applicable to high-frequency communication electronic components. Attached Figure Description

[0023] Figure 1 This is a synthetic route diagram of the gelatin-based polymer molecular brush PB1 in Example 1;

[0024] Figure 2 This is a synthetic route diagram of the gelatin-based polymer molecular brush PB2 in Example 2;

[0025] Figure 3 This is a synthetic route diagram of the gelatin-based polymer molecular brush PB3 in Example 3;

[0026] Figure 4 This is a schematic diagram of the peel strength test plate being pressed together;

[0027] Figure 5 This is a schematic diagram of the reflow soldering test board pressing.

[0028] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Furthermore, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., described below refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the technical features involved in the various embodiments of the invention can be combined with each other as long as they do not conflict with each other.

[0030] This invention provides a gelatin-based polymer molecular brush having a structure as shown in structural formula (I) or (II):

[0031] Formula (I) or Formula (II);

[0032] Wherein, n represents the number of methylene groups, and is an integer from 0 to 12. Preferably, n is an integer from 1 to 5.

[0033] Furthermore, the gelatin-based polymer molecular brush is a product having a structure as shown in structural formula (I) or (II) and its catechol groups after oxidation, coordination, and crosslinking.

[0034] The preparation method of the gelatin-based polymer molecular brush includes the following steps: in a solvent, compound A having structural formula (III) and compound B having general formula (IV) or compound C having general formula (V) are polymerized by heating reaction.

[0035] Equation (III)

[0036] Formula (IV) or Formula (V);

[0037] Where n represents the number of methylene groups, which is an integer from 0 to 12.

[0038] Specifically, the solvent does not react with compounds A, B, and C, and the solvent includes any one of hydrocarbon solvents, alcohol solvents, amide solvents, ketone solvents, ether solvents, ester solvents, acetonitrile, and dimethyl sulfoxide. Specifically, the hydrocarbon solvent includes any one of toluene, xylene, and n-hexane; the alcohol solvent includes any one of methanol and ethanol; the amide solvent includes any one of N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; the ketone solvent includes any one of acetone and cyclohexanone; the ether solvent includes any one of diethyl ether, tetrahydrofuran, and 1,4-dioxane; and the ester solvent includes any one of ethyl acetate and butyl acetate.

[0039] Preferably, in the preparation process of the heating reaction, the mass ratio of the substance with structural formula (I) to the compound having the structure shown in general formula (IV) or (V) is 1:(5-20). Further, the mass ratio of the substance with structural formula (I) to the compound having the structure shown in general formula (IV) or (V) is 1:(5-15). Preferably, the heating reaction temperature is 30-120°C. More preferably, the heating reaction temperature is 60-120°C. The heating reaction time is 3-24 hours. More preferably, the heating reaction time is 6-12 hours.

[0040] Specifically, compound B includes any one of 3,4-dihydroxybenzaldehyde, 3,4-dihydroxyphenylacetaldehyde, and 3-(3,4-dihydroxyphenyl)propanal. Compound C includes any one of 3,4-dihydroxybenzoic acid, 3,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylpropionic acid, 4-(3,4-dihydroxyphenyl)butyric acid, and 5-(3,4-dihydroxyphenyl)valerate.

[0041] Gelatin-based polymer molecular brushes with structures as shown in general formulas (I) and (II) can exhibit a variety of adhesive effects, as illustrated in the following pathways:

[0042]

[0043]

[0044] As can be seen from the above route, the gelatin-based polymer molecular brush with the structure shown in general formulas (I) and (II) provided in this application has the following effects: it can adhere to adjacent dopa molecules through intermolecular hydrogen bonds; it can adhere to metal cations through coordination; it can adhere to dopa molecules through π-π interactions; it can adhere to thiol reduction; it can condense through cation-π interactions; and the hydroxyl groups can be oxidized and then condense intermolecularly.

[0045] This invention also provides a surface treatment liquid, comprising an organic solvent and / or water, and the aforementioned gelatin-based polymer molecular brush. The organic solvent includes any one of methanol, ethanol, 1-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, diethylene glycol, glycerol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol methyl ether, ethylene glycol monobutyl ether, N-methylpyrrolidone, dimethyl sulfoxide, benzene, toluene, xylene, n-hexane, cyclohexane, dichloromethane, chloroform, dichlorobenzene, acetone, and butanone. In the preparation of the surface treatment liquid, the desired surface treatment liquid can be obtained by dissolving the gelatin-based polymer molecular brush in the organic solvent and / or water.

[0046] The surface treatment liquid provided by this invention can be used to treat the surface of materials, forming an organic film on the material surface and improving adhesion to other materials. The contact time between the surface treatment liquid and the material is designed to allow the liquid to interact with the material surface, preferably 10 seconds to 1 hour, more preferably 30 seconds to 30 minutes. The temperature of the surface treatment liquid during material contact is preferably 20°C to 50°C, more preferably 25°C to 35°C. After contact with the material, the surface treatment liquid can be left to stand at room temperature, or it can be directly dried with cold or hot air, or dried at 70°C to 150°C.

[0047] Specifically, the material may be selected from inorganic materials and / or resin materials, and its shape is not limited. The inorganic material is selected from any one of metals, metal oxides, silicon-containing materials, ceramics, and magnetic materials. The resin material is selected from any one of acrylic resins, epoxy resins, modified epoxy resins, polyimide resins, modified polyimide resins, liquid crystal polymers, polyphenylene ether resins, polyphenylene sulfide resins, hydrocarbon resins, and polytetrafluoroethylene resins. The metal is selected from any one of copper, aluminum, titanium, nickel, tin, iron, silver, gold, and their alloys. The metal oxide is selected from any one of copper oxide, cuprous oxide, iron oxide, calcium oxide, sodium oxide, magnesium oxide, barium oxide, aluminum oxide, zinc oxide, manganese heptaoxide, manganese zinc ferrite, and nickel zinc ferrite. The silicon-containing material is selected from any one of silicon, glass, silicon carbide, silicon dioxide, glass, and diatomaceous earth. The ceramic contains any one of nitrogen boride, titanium boride, zirconium boride, magnesium titanate, calcium titanate, barium titanate, aluminum nitride, and silicon nitride.

[0048] This invention also provides the application of surface treatment liquid in semiconductor device processing. The surface treatment liquid in semiconductor device processing includes the following specific steps: contacting the surface treatment liquid with the surface of a first material to form a thin film, and then bonding it to a second material; wherein the contact method is spraying or immersion, and the first and second materials are respectively selected from inorganic materials and / or resin materials.

[0049] The gelatin-based polymer molecular brush provided by this invention can be used as the main component of a surface treatment liquid for bonding materials. This ensures the peel strength between materials and improves the bonding force without the need for browning treatment of the material surface. It also has good heat resistance and can be applied to the manufacture of PCBs, such as the manufacture of multilayer laminates, the preparation of semiconductor components, and high-frequency communication electronic components, such as the bonding or metallization of dielectric ceramics.

[0050] Example 1

[0051] 1.2 g of type A gelatin (purchased from Sigma-Aldrich) was dissolved in 12 mL of N,N-dimethylformamide at 80 °C to prepare a homogeneous solution (10% w / v). Then, 12 g of 3,4-dihydroxybenzaldehyde was added, and the mixture was stirred until completely dissolved and reacted for 24 hours. The reaction solution was then cooled to room temperature and transferred to an 8-14 kDa cutoff dialysis bag. Dialysis was performed at 50 °C with deionized water for 3 days, changing the deionized water every 6 hours to remove unreacted raw materials and byproducts. The gelatin-based polymer molecule PB1 was then frozen at -80 °C and stored at room temperature to obtain a pale yellow oily substance (3.8 g).

[0052] The molecular weights of gelatin and the polymer molecular brush PB1 after the reaction were tested separately. The average molecular weight of type A gelatin was 41,200, and the average molecular weight of the polymer molecular brush was 42,100. According to the gel permeation chromatography test results, the oily substance obtained in this example is the gelatin-based polymer molecular brush PB1 shown in the reaction formula.

[0053] The synthetic route of PB1 is as follows: Figure 1 .

[0054] Example 2

[0055] 0.8 g of type A gelatin (purchased from Sigma-Aldrich) was dissolved in 8 mL of N,N-dimethylformamide at 80 °C to prepare a homogeneous solution at 10% w / v. Then, 8 g of 3,4-dihydroxybenzoic acid was added, and the mixture was stirred until completely dissolved and reacted for 24 hours. The reaction solution was then cooled to room temperature and transferred to an 8-14 kDa cutoff dialysis bag. Dialysis was performed at 50 °C with deionized water for 4 days, changing the deionized water every 6 hours to remove unreacted raw materials and byproducts. The gelatin-based polymer molecule PB3 was then frozen at -80 °C and stored at room temperature to obtain a white oily substance (4.2 g).

[0056] The molecular weights of gelatin and the polymer molecular brush PB2 after the reaction were tested separately. The average molecular weight of type A gelatin was 41,200, and the average molecular weight of the polymer molecular brush was 42,900. According to the gel permeation chromatography test results, the oily substance obtained in this example is the gelatin-based polymer molecular brush PB2 shown in the reaction formula.

[0057] The synthetic route of PB2 is as follows: Figure 2 .

[0058] Example 3

[0059] 0.8 g of type A gelatin (purchased from Sigma-Aldrich) was dissolved in 8 mL of N,N-dimethylformamide at 80 °C to prepare a homogeneous solution (10% w / v). Then, 8 g of 3,4-dihydroxybenzoic acid was added, and the mixture was stirred until completely dissolved and reacted for 24 hours. The reaction solution was then cooled to room temperature and transferred to an 8-14 kDa cutoff dialysis bag. Dialysis was performed at 50 °C with deionized water for 4 days, changing the deionized water every 6 hours to remove unreacted raw materials and byproducts. The gelatin polymer molecular brush PB3 was then frozen at -80 °C and stored at room temperature to obtain a white oily substance (4.2 g).

[0060] The molecular weights of gelatin and the polymer molecular brush PB3 after the reaction were tested separately. The average molecular weight of type A gelatin was 41,200, and the average molecular weight of the polymer molecular brush was 43,300. According to the gel permeation chromatography test results, the oily substance obtained in this example is the gelatin-based polymer molecular brush PB3 shown in the reaction formula.

[0061] The synthetic route of PB3 is as follows: Figure 3 .

[0062] Effect test experiment:

[0063] (1) Preparation of surface treatment solution

[0064] The gelatin-based polymer molecular brushes prepared in Examples 1-3 and 4-(aminomethyl)phenyl-1,2-diol (without nitrogen heterocyclic structure) are provided. 5g of each of the four raw materials are dissolved in 250g of ethylene glycol monobutyl ether, and then 250g of deionized water is added to each. The mixtures are stirred at room temperature for 24 hours to prepare surface treatment solutions A, B, C, and D, respectively. A blank surface treatment solution E is prepared, containing only 250g of ethylene glycol monobutyl ether and 250g of deionized water, without any dopa (3,4-dihydroxyphenylalanine) compound. All the above surface treatment solutions are for later use. 4-(aminomethyl)phenyl-1,2-diol is an organic compound with a benzene ring containing an aminomethyl group (-CH2NH2) and two adjacent hydroxyl groups (-OH), which facilitates the formation of hydrogen bonds or electrostatic interactions. It can be used to enhance the adhesion between polymers and material surfaces and has wide applications in surface modification and adhesive layer formation. In the comparative experiment, 4-(aminomethyl)benzene-1,2-diol was introduced to evaluate its effect on enhancing adhesion and to compare it with the gelatin-based polymer molecular brush provided in this invention.

[0065] (2) Processing flow

[0066] Pickling (room temperature, 60 seconds) — water rinse — alkaline pickling (30℃, 60 seconds) — water rinse — surface treatment solution (30℃, 60 seconds) — water rinse — drying (100℃, 10 minutes).

[0067] (3) Fabrication of the test board

[0068] 1. The peel strength test involves placing M6 resin (polyphenylene ether resin) on a standard copper-clad laminate, then placing the smooth side of the standard copper foil treated with the aforementioned surface treatment solution facing the resin, with the pressing structure as follows: Figure 4 As shown, the final pressing is performed according to the pressing conditions of M6 resin.

[0069] 2. The heat resistance (lead-free reflow soldering) test involves placing M6 resin (polyphenylene ether resin) on a standard copper-clad laminate that has undergone surface treatment, with the rough side of the standard copper foil facing the resin. The lamination structure is as follows: Figure 5 As shown, the final pressing is performed according to the pressing conditions of M6 resin.

[0070] (4) Adhesion evaluation test

[0071] The peel strength was determined using a 7cm x 8cm ordinary electrolytic copper foil (1 ounce) according to the standard “IPC-TM-650 No.2.4.8”.

[0072] (5) Heat resistance evaluation test

[0073] Heat resistance (lead-free reflow soldering) was determined using a 7cm x 8cm ordinary electrolytic copper foil (1 ounce) in accordance with standard “IPC-TM-650 No.2.6.8”.

[0074] The test results are shown in Table 1:

[0075] Table 1. Test data results of polymer molecular brushes

[0076]

[0077] The above results show that the bonding strength between adhesive materials treated with the nitrogen-containing heterocyclic dopa compound of the present invention is greater than 3.0 Ib / in, and the number of reflow soldering (thermal shock) cycles is more than 10, indicating that the adhesive materials obtained after treatment with the surface treatment liquid provided by the present invention have good mechanical properties and thermal stability. In contrast, the adhesive materials treated with 4-(aminomethyl)benzene-1,2-diol (without nitrogen heterocycles), although they can provide some adhesion, are far less effective than the gelatin-based polymer molecular brush provided by the present invention, and the mechanical properties and thermal stability of the treated adhesive materials do not meet the requirements. Treating the materials with a blank treatment liquid containing no polymer molecular brushes does not result in any bonding ability or thermal stability in the adhesive materials. The adhesive materials obtained after treatment with the gelatin-based polymer molecular brush provided in this application can still achieve good mechanical properties and thermal stability without the need for browning treatment by immersing the PCB substrate in a browning solution.

[0078] In summary, the gelatin-based polymer molecular brush provided by this invention improves the mechanical strength of gelatin-based materials by introducing a specific chemical structure, making it more suitable for applications requiring high-strength materials. This gelatin-based polymer molecular brush can be used as a main component of surface treatment liquids for bonding materials, ensuring peel strength and improving adhesion without the need for surface browning treatment. It also exhibits good heat resistance and can be used in the processing of semiconductor devices, especially in the manufacture of multilayer PCBs, providing higher-performance semiconductor devices and enabling applications in high-frequency communication electronic components.

[0079] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. Use of a surface treatment liquid in the processing of semiconductor devices, characterized in that, The surface treatment liquid comprises an organic solvent and / or water, and a gelatin-like polymer molecular brush having a structure as shown in formula (I) or (II): Formula (I) or Formula (II); wherein n represents the number of methylene groups, and is an integer from 0 to 12; the preparation method of the gelatin-like polymer molecular brush comprises the following steps: in a solvent, compound A having formula (III) and compound B having general formula (IV) or compound C having general formula (V) are polymerized by heating reaction, Formula (III) Formula (IV) or Formula (V); wherein n represents the number of methylene groups, and is an integer from 0 to 12, the compound B comprises any one of 3,4-dihydroxybenzaldehyde, 3,4-dihydroxyphenylacetaldehyde and 3-(3,4-dihydroxyphenyl)propionaldehyde, and the compound C comprises any one of 3,4-dihydroxybenzoic acid, 3,4-dihydroxyphenylacetic acid, 3,4-dihydroxyphenylpropionic acid, 4-(3,4-dihydroxyphenyl)butyric acid and 5-(3,4-dihydroxyphenyl)valeric acid.

2. The use of the surface treatment liquid according to claim 1 in the processing of semiconductor devices, characterized in that, The gelatin-like polymer molecular brush has a structure as shown in formula (I) or (II) and the product after oxidation, coordination and cross-linking of the pyrocatechol group thereof.

3. The use of the surface treatment liquid according to claim 1 in the processing of semiconductor devices, characterized in that, The solvent does not react with the compound A, the compound B and the compound C, and the solvent comprises any one of a hydrocarbon solvent, an alcohol solvent, an amide solvent, a ketone solvent, an ether solvent, an ester solvent, acetonitrile and dimethyl sulfoxide.

4. The use of the surface treatment liquid according to claim 1 in the processing of semiconductor devices, characterized in that, The organic solvent comprises any one of methanol, ethanol, 1-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, diethylene glycol, glycerol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol methyl ether, ethylene glycol monobutyl ether, N-methyl pyrrolidone, dimethyl sulfoxide, benzene, toluene, xylene, n-hexane, cyclohexane, dichloromethane, chloroform, dichlorobenzene, acetone and butanone.

5. The use of the surface treatment liquid according to claim 1 in semiconductor device processing, characterized by, The surface treatment liquid is used in processing of a semiconductor device, and the processing comprises the following specific steps: contacting the surface treatment liquid with a surface of a first material, forming a thin film and then adhering to a second material; wherein the contacting method is spraying or immersion, and the first material and the second material are selected from inorganic materials and / or resin materials.

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