A cutting protection liquid, preparation method and application thereof

Abstract

The present application discloses a cutting protection liquid, a preparation method and application thereof, wherein the cutting protection liquid comprises a polymer and an organic solvent; the polymer comprises a first molecular chain bonded with an alkoxysilane, a second molecular chain bonded with a hydrophobic group and a third molecular chain bonded with a hydrophilic group, and the first molecular chain, the second molecular chain and the third molecular chain are connected in sequence. The cutting protection liquid can adapt to substrates of different shapes, adhere to the surface of the substrate, and form a complete protective film on the surface of the substrate; and the protective film is alkali-sensitive, and after the cutting process is completed, the protective film can be completely removed by an alkaline solvent, and the cleaning process is simple.

Description

Technical Field

[0001] The present application belongs to the field of chip cutting technology, and specifically relates to a cutting protection liquid, a preparation method and application thereof. Background Art

[0002] GaAs-based chips generally have a high aspect ratio structure. When laser cutting protective fluid is used on chips with a high aspect ratio structure, there will be problems such as the bottom cutting path bursting or the step edge failing to protect the slag residue. Therefore, it is necessary to develop a laser cutting protective fluid that can simultaneously protect the bottom cutting path and step edge of the GaAs chip. Summary of the invention

[0003] Purpose of application: This application provides a cutting protection liquid, its preparation method and application, aiming to simultaneously protect the cutting path and step edge at the bottom of the GaAs chip, and improve the yield and productivity in the semiconductor manufacturing process.

[0004] Technical solution: A cutting protection liquid of the present application includes a high molecular polymer and an organic solvent; the high molecular polymer has a first molecular chain bonded with an alkoxysilane, a second molecular chain bonded with a hydrophobic group and a third molecular chain bonded with a hydrophilic group, and the first molecular chain, the second molecular chain and the third molecular chain are connected in sequence.

[0005] In some embodiments, the alkoxysilane is selected from at least one of methoxysilane, ethoxysilane and propoxysilane; and / or

[0006] The hydrophobic group is selected from at least one of a methyl group and an ethyl group; and / or

[0007] The hydrophilic group is selected from at least one of an ester group, a carboxyl group, and a hydroxyl group.

[0008] In some embodiments, the first molecular chain is selected from the structural units of olefins; the second molecular chain is selected from the structural units of acrylic acid; and the third molecular chain is selected from the structural units of acrylic acid.

[0009] In some embodiments, the composition comprises, by weight: 8 to 35 parts of a high molecular weight polymer, 50 to 100 parts of an organic solvent, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles, and 0.1 to 0.5 parts of an ultraviolet absorber.

[0010] In some embodiments, the molecular weight of the polymer is 5000 to 50000; and / or

[0011] The toughening agent is selected from at least one of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber, polysulfide rubber, liquid silicone rubber, carboxyl nitrile rubber, chloroprene rubber, and acrylate rubber; and / or

[0012] The inorganic particles are selected from at least one of nano calcium carbonate, nano silicon dioxide and nano titanium dioxide; and / or

[0013] The ultraviolet absorber is at least one selected from the group consisting of sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate, phenyl o-hydroxybenzoate, and o-nitroaniline; and / or

[0014] The organic solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, ethyl ether, methyl ethyl ether, di-n-butyl ether, propylene glycol methyl ether, ethylene glycol propyl ether, ethyl acetate and n-butyl acetate.

[0015] In some embodiments, the toughening agent is selected from acrylate rubber, the inorganic particles are selected from nano-calcium carbonate, and the mass ratio of the acrylate rubber to the nano-calcium carbonate is (100-500):1; and / or

[0016] The organic solvent is selected from isopropanol and propylene glycol methyl ether, and the mass ratio of the isopropanol to the propylene glycol methyl ether is (1-20):1.

[0017] In some embodiments, the present application also provides a method for preparing a cutting protection liquid, comprising the following steps:

[0018] Step 1: Mix a reaction solvent, a first monomer, a second monomer, and a third monomer, and then add an initiator to react to obtain a high molecular weight polymer;

[0019] Step 2: Weigh 8 to 35 parts of a high molecular polymer, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles, 0.1 to 0.5 parts of an ultraviolet absorber and 50 to 100 parts of an organic solvent, mix and stir, and prepare a cutting protection liquid.

[0020] In some embodiments, the first monomer is selected from at least one of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane;

[0021] The second monomer is selected from at least one of methyl methacrylate, lauryl methacrylate, butyl methacrylate, and octadecyl methacrylate;

[0022] The third monomer is selected from at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.

[0023] In some embodiments, the molar ratio of the first monomer, the second monomer, the third monomer, the initiator and the ethyl acetate is (1-5): (1-10): (1-5): (0.01-0.05) : (15-20);

[0024] In the step 1, the reaction temperature is 50-110°C and the reaction time is 6-8h;

[0025] In the step 2, the stirring speed is 200-500 rpm, and the stirring time is 1-5 h.

[0026] In some embodiments, the present application also provides application of the cutting protection liquid in wafer cutting.

[0027] Beneficial effect: Compared with the prior art, the cutting protection liquid of the present application includes a first molecular chain having alkoxysilane, a second molecular chain having a hydrophobic group and a third molecular chain having a hydrophilic group, wherein the alkoxysilane improves the adhesion of the cutting protection liquid, the hydrophobic group improves the water resistance of the cutting protection liquid, and the hydrophilic group improves the film-forming property of the cutting protection liquid. The cutting protection liquid can adapt to substrates of different shapes, adhere to the surface of the substrate, and form a complete protective film on the surface of the substrate; and the protective film is alkali-sensitive. After the cutting process is completed, the protective film can be completely removed by an alkaline solvent, and the cleaning process is simple.

[0028] It can be understood that, compared with the prior art, the preparation method of the cutting protection liquid and the application of the cutting protection liquid provided in the embodiments of the present application have all the technical features and beneficial effects of the above-mentioned composition, which will not be repeated here. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.

[0030] Figure 1 This is a microscope picture with a magnification of 500 times after coating with the cutting protection liquid of Example 9;

[0031] Figure 2 This is a microscope picture with a magnification of 500 times after coating with the cutting protection liquid of Comparative Example 1;

[0032] Figure 3 This is the ultraviolet spectrum of the cutting protection liquid in Example 9. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0034] In the description of the present application, it should be noted that, unless otherwise clearly specified and limited, the terms "connected" and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection, an electrical connection, or can communicate with each other; it can be directly connected, or indirectly connected through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to the specific circumstances. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined. In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more features.

[0035] The disclosure below provides many different embodiments or examples to realize the different structures of the present application. In order to simplify the disclosure of the present application, the parts and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the present application.

[0036] The applicant found that part of the product types of domestic third-generation semiconductor companies are GaAs-based chips, in which the chip structure generally has a high aspect ratio structure. It is common that there will be a layer of steps on the cutting path, the width of the cutting path varies from 25-65μm, and the step height varies from 9-20μm. When the laser cutting protection fluid is used on chips with high aspect ratio structures, there will be problems such as the bottom cutting path bursting or the step edge cannot be protected, and slag residue. There is currently no very good solution for this type of chip laser protection fluid. Therefore, it is urgent to develop a laser cutting protection fluid that can simultaneously protect the bottom cutting path and step edge of the GaAs chip.

[0037] An embodiment of the present application provides a cutting protection liquid, including a high molecular polymer and an organic solvent; the high molecular polymer has a first molecular chain bonded with alkoxysilane, a second molecular chain bonded with a hydrophobic group and a third molecular chain bonded with a hydrophilic group, and the first molecular chain, the second molecular chain and the third molecular chain are connected in sequence.

[0038] It is understandable that the cutting protection liquid of the present application is adaptable to substrates of different shapes, adheres to the surface of the substrate, and forms a complete protective film on the surface of the substrate. The reason why the above effect can be achieved is that the high molecular polymer has alkoxysilane, hydrophobic group and hydrophilic group at the same time; wherein, alkoxysilane improves the adhesion of the polymer to the substrate through the molecular bridge effect, and alkoxysilane can react with the polymer to bind the alkoxysilane group to the main chain of the polymer, and then can react with water vapor to achieve cross-linking and form a stable three-dimensional body structure. Since a network structure is formed after polymerization, the strength and elasticity of the polymer can also be improved, and the adhesion of the polymer is also enhanced, which can firmly protect the substrate; the hydrophobic group can form a hydrophobic layer on the surface of the cutting liquid to prevent the cutting liquid from being dissolved by water during cutting; the hydrophilic group improves the flexibility of the high molecular polymer in the cutting liquid, promotes the film formation of the high molecular polymer on the surface of the substrate, makes the formed film softer, and enhances the coating force.

[0039] Furthermore, the cutting protection liquid can adapt to substrates of different shapes, adhere to the surface of the substrate, and form a complete protective film on the surface of the substrate; when the cutting liquid is coated on the surface of the chip, the protective film formed is alkali-sensitive. After the cutting process is completed, the protective film can be completely removed by an alkaline solvent, and the cleaning process is simple.

[0040] In some embodiments, the alkoxysilane is selected from at least one of methoxysilane, ethoxysilane and propoxysilane. It is understood that the silane with a hydrophobic organic group on the silicon atom of the alkoxysilane can further cooperate with other hydrophobic groups to impart hydrophobic properties to the cutting fluid surface.

[0041] In some embodiments, the hydrophobic group is selected from at least one of a methyl group and an ethyl group, preferably a methyl group.

[0042] In some embodiments, the hydrophilic group is selected from at least one of an ester group, a carboxyl group, and a hydroxyl group, preferably an ester group.

[0043] In some embodiments, the high molecular polymer is a copolymer resin; preferably, the high molecular polymer is an acrylic resin with cross-linking points introduced into the side chain. The first molecular chain is selected from the structural unit of olefins, for example, the monomer corresponding to the first molecular chain can be γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane; the second molecular chain is selected from the structural unit of acrylic acid, for example, the monomer corresponding to the second molecular chain can be methyl methacrylate, lauryl methacrylate, butyl methacrylate, octadecyl methacrylate; the third molecular chain is selected from the structural unit of acrylic acid, for example, the monomer corresponding to the third molecular chain can be ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate.

[0044] Furthermore, in addition to the hydrophobic group, the second molecular chain can also be connected to a hydrophilic group, such as an ester group; by connecting other hydrophilic groups to the second molecular chain, the flexibility of the polymer can be further improved, and the adhesion of the cutting protection liquid film on the substrate surface can be improved.

[0045] Furthermore, the cutting protection liquid includes, by weight, 8 to 35 parts of a high molecular polymer, 50 to 100 parts of an organic solvent, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles and 0.1 to 0.5 parts of an ultraviolet absorber.

[0046] In some embodiments, the cutting protection liquid includes, by weight: 12 to 18 parts of a high molecular polymer, 70 to 85 parts of an organic solvent, 0.5 to 1.5 parts of a toughening agent, 0.002 to 0.003 parts of inorganic particles, and 0.2 to 0.4 parts of an ultraviolet absorber.

[0047] In some embodiments, the molecular weight of the polymer is 5000 to 50000, preferably 20000 to 30000. The polymerization conditions are controlled to make the molecular weight of the polymer between 20000 and 30000. Within this molecular weight range, the polymer has excellent film-forming properties and can be adapted to substrates of different shapes.

[0048] In some embodiments, the toughening agent is selected from at least one of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber, polysulfide rubber, liquid silicone rubber, carboxyl nitrile rubber, chloroprene rubber, and acrylate rubber. The toughening agent can increase the flexibility of the film layer. By miscible toughening agent with high molecular polymer, the active groups therein can participate in curing, thereby improving the overall elongation at break and impact strength. The preferred toughening agent is acrylate rubber, because acrylate rubber and high molecular polymer belong to the acrylic acid series, have high compatibility, and can further increase the flexibility of the film layer, so that the film layer can be better softly coated with the complex structure of the substrate, reduce its brittleness, and prevent the film layer from breaking.

[0049] In some embodiments, in order to further improve the dispersion effect of the toughening agent in the high molecular polymer, the cutting protection liquid also includes inorganic particles, and the inorganic particles are selected from at least one of nano calcium carbonate, nano silicon dioxide, and nano titanium dioxide; among them, the preferred inorganic particles are nano calcium carbonate, because nano calcium carbonate is nano-scale and has a smaller particle size, and can be evenly dispersed in the protection liquid, and work together with the high molecular polymer to form a protective film.

[0050] In some embodiments, the ultraviolet absorber is selected from at least one of 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate sodium, o-hydroxybenzoic acid phenyl ester, and o-nitroaniline; the ultraviolet absorber is a light stabilizer that can absorb the ultraviolet part of sunlight and fluorescent light sources without changing itself. The ultraviolet absorber is used to effectively protect the cutting protection material and weaken the damage of ultraviolet rays to it. The preferred ultraviolet absorber is 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate sodium with two benzene rings. It has two conjugated benzene rings, has extremely high solubility in a mixed solvent of propylene glycol methyl ether and isopropanol, has good compatibility with high molecular polymers, can be evenly dispersed in the material, and has an obvious absorption peak at 350nm after being prepared into a protective solution, which has a better cutting effect, and has good chemical stability and does not react adversely with material components.

[0051] In certain embodiments, the organic solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, ether, methyl ethyl ether, di-n-butyl ether, propylene glycol methyl ether, ethylene glycol propyl ether, ethyl acetate, and n-butyl acetate. The organic solvent is preferably a combination of isopropanol and propylene glycol methyl ether, the flash point of isopropanol is 11.7 ° C, it is easy to evaporate and dry to form a film quickly, and the propylene glycol methyl ether molecule contains both alcohol and ether functional groups, which can provide unique polar and non-polar solubility, and isopropanol has good compatibility. Wherein, the mass ratio of isopropanol to propylene glycol methyl ether is (1-20): 1, for example, the mass ratio of isopropanol to propylene glycol methyl ether can be any ratio in 1: 1, 2: 1, 5: 1, 8: 1, 10: 1, 12: 1, 15: 1, 18: 1, 20: 1 or the range between any two ratios.

[0052] In some embodiments, the toughening agent is selected from acrylic rubber, the inorganic particles are selected from nano-calcium carbonate, and the mass ratio of acrylic rubber to nano-calcium carbonate is (100-500):1. For example, the mass ratio of acrylic rubber to nano-calcium carbonate can be any ratio of 100:1, 200:1, 300:1, 400:1, 500:1 or a range between any two ratios.

[0053] The present application also provides a method for preparing a cutting protection liquid, comprising the following steps:

[0054] Step 1: Mix a reaction solvent, a first monomer, a second monomer, and a third monomer, and then add an initiator to react to obtain a high molecular weight polymer;

[0055] Step 2: Weigh 8 to 35 parts of a high molecular polymer, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles, 0.1 to 0.5 parts of an ultraviolet absorber and 50 to 100 parts of an organic solvent, mix and stir, and prepare a cutting protection liquid.

[0056] In some embodiments, in step one, the reaction temperature is 50-110°C, and the reaction time is 6-8h; for example, the reaction temperature is any one of 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or a range between any two values; the reaction time is any one of 6h, 7h, 8h, or a range between any two values.

[0057] In some embodiments, in step 2, the stirring speed is 200-500rpm, and the stirring time is 1-5h; for example, the stirring speed is any one of 200rpm, 300rpm, 400rpm, 500rpm, or a range between any two values; the stirring time is any one of 1h, 2h, 3h, 4h, 5h, or a range between any two values.

[0058] In some embodiments, the first monomer is selected from at least one of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane.

[0059] In some embodiments, the high molecular weight polymer is preferably prepared by copolymerization of methyl methacrylate, ethyl acrylate, and γ-methacryloxypropyltrimethoxysilane.

[0060] In some embodiments, the second monomer is selected from at least one of methyl methacrylate, lauryl methacrylate, butyl methacrylate, and octadecyl methacrylate.

[0061] In some embodiments, the third monomer is selected from at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.

[0062] In some embodiments, the molar ratio of the first monomer, the second monomer, the third monomer, the initiator and the ethyl acetate is (1-5):(1-10):(1-5):(0.01-0.05):(15-20).

[0063] In some embodiments, the initiator may be azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, ammonium persulfate, etc., preferably azobisisobutyronitrile and benzoyl peroxide, and most preferably azobisisobutyronitrile.

[0064] In some embodiments, the method for preparing the cutting protection liquid specifically includes:

[0065] Weigh the high molecular polymer, toughening agent, ultraviolet absorber, inorganic particles and organic solvent respectively by weight;

[0066] Each component is added into a mixing container equipped with a stirrer, and stirred at a speed of 200 to 500 rpm for 1 to 5 hours at room temperature to obtain a cutting protection liquid. Here, room temperature specifically refers to 25°C.

[0067] In some embodiments, the present application also provides a method for using the cutting protection liquid, which is as follows:

[0068] First, clean the chips of different sizes to be coated;

[0069] Set up the spin coating program and drip the cutting protection material on the chip. The dosage includes: 10ml / 4 inch, 15ml / 6 inch, 25ml / 8 inch, 35ml / 12 inch, etc. Spin coating at 1000rpm for 2 minutes;

[0070] After spin coating, the next cutting process can be carried out.

[0071] In some embodiments, the cutting protection liquid can be applied to the cutting protection of chips, especially GaAs chips, and can simultaneously protect the cutting path and step edge at the bottom of the GaAs chip; it can adapt to various wafer structures, and form a protective film on the surface of the wafer to ensure that the wafer is not scratched by debris during the cutting process, so as to improve the yield of semiconductor products and the efficiency of cutting. Therefore, the cutting protection liquid of the present application has very good application prospects and large-scale industrial promotion potential in the field of semiconductor cutting protection.

[0072] It can be understood that the wafer here refers to a wafer with a chip structure on its surface, and chips can be obtained after cutting the wafer.

[0073] Example 1

[0074] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and the reaction is stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 1:4:1:0.03:16; the first monomer is γ-methacryloxypropyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisobutyronitrile.

[0075] Example 2

[0076] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and the reaction is stirred at 50°C for 8 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 2:1:5:0.01:15; the first monomer is vinyl trimethoxysilane, the second monomer is butyl methacrylate, the third monomer is butyl acrylate, and the initiator is azobisisoheptonitrile.

[0077] Example 3

[0078] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is used as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and stirred at 110°C for 6 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 3:5:2:0.02:17; the first monomer is vinyl triethoxysilane, the second monomer is lauryl methacrylate, the third monomer is lauryl acrylate, and the initiator is benzoyl peroxide.

[0079] Example 4

[0080] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and the reaction is stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 4:6:3:0.03:18; the first monomer is vinyl triisopropoxy silane, the second monomer is octadecyl methacrylate, the third monomer is 2-ethylhexyl acrylate, and the initiator is ammonium persulfate.

[0081] Example 5

[0082] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and the reaction is stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 1:10:1:0.01:15; the first monomer is γ-methacryloxypropyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisoheptonitrile.

[0083] Example 6

[0084] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 5:10:5:0.05:20; the first monomer is γ-methacryloxypropyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is benzoyl peroxide.

[0085] Example 7

[0086] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is taken as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 4:9:3:0.02:15; the first monomer is γ-methacryloxypropyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is ammonium persulfate.

[0087] Example 8

[0088] Provided is a high molecular polymer, and the specific preparation process is: under nitrogen protection, ethyl acetate is used as a reaction solvent, and then a first monomer, a second monomer, a third monomer and an initiator are added to the ethyl acetate, and the reaction is stirred at 80°C for 7 hours to obtain a high molecular polymer. The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and ethyl acetate is 3:2:3:0.04:17; the first monomer is γ-methacryloxypropyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisoheptonitrile.

[0089] Example 9

[0090] Provided is a cutting protection liquid, comprising: 15 parts of a high molecular polymer, 80 parts of an organic solvent, 1 part of a toughening agent, 0.005 parts of inorganic particles and 0.3 parts of an ultraviolet absorber;

[0091] Among them, the high molecular polymer is the high molecular polymer provided in Example 1, the organic solvent is isopropyl alcohol and propylene glycol methyl ether in a mass ratio of 4:1, the toughening agent is acrylic rubber, the inorganic particles are nano-calcium carbonate, and the ultraviolet absorber is 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate sodium.

[0092] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 400 rpm for 2 hours to obtain the cutting protection liquid.

[0093] Example 10

[0094] Provided is a cutting protection liquid, comprising: 12 parts of a high molecular polymer, 70 parts of an organic solvent, 0.5 parts of a toughening agent, 0.005 parts of inorganic particles and 0.2 parts of an ultraviolet absorber;

[0095] Among them, the high molecular polymer is the high molecular polymer provided in Example 2, the organic solvent is isopropyl alcohol and propylene glycol methyl ether in a mass ratio of 1:1, the toughening agent is carboxyl liquid nitrile rubber, the inorganic particles are nano-silica, and the ultraviolet absorber is phenyl o-hydroxybenzoate.

[0096] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective parts by mass, and stir at a speed of 500 rpm for 1 hour to obtain the cutting protection liquid.

[0097] Embodiment 11

[0098] Provided is a cutting protection liquid, comprising: 18 parts of a high molecular polymer, 85 parts of an organic solvent, 1.5 parts of a toughening agent, 0.005 parts of inorganic particles and 0.4 parts of an ultraviolet absorber;

[0099] Among them, the high molecular polymer is the high molecular polymer provided in Example 3, the organic solvent is isopropyl alcohol and propylene glycol methyl ether in a mass ratio of 16:1, the toughening agent is carboxyl-terminated liquid nitrile rubber, the inorganic particles are nano titanium dioxide, and the ultraviolet absorber is o-nitroaniline.

[0100] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective parts by mass, and stir at a speed of 300 rpm for 3 hours to obtain the cutting protection liquid.

[0101] Example 12

[0102] Provided is a cutting protection liquid, comprising: 8 parts of a high molecular polymer, 50 parts of an organic solvent, 0.1 parts of a toughening agent, 0.001 parts of inorganic particles and 0.1 parts of an ultraviolet absorber;

[0103] Among them, the high molecular polymer is the high molecular polymer provided in Example 4, the organic solvent is ethanol and ethylene glycol propyl ether in a mass ratio of 4:1, the toughening agent is polysulfide rubber, the inorganic particles are nano-calcium carbonate, and the ultraviolet absorber is phenyl o-hydroxybenzoate.

[0104] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 200 rpm for 4 hours to obtain the cutting protection liquid.

[0105] Example 13

[0106] Provided is a cutting protection liquid, comprising: 35 parts of a high molecular polymer, 100 parts of an organic solvent, 2 parts of a toughening agent, 0.004 parts of inorganic particles and 0.5 parts of an ultraviolet absorber;

[0107] The high molecular polymer is the high molecular polymer provided in Example 5, the organic solvent is tert-butyl alcohol and n-butyl acetate in a mass ratio of 9:1, the toughening agent is liquid silicone rubber, the inorganic particles are nano-titanium dioxide, and the ultraviolet absorber is o-nitroaniline.

[0108] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 300 rpm for 5 hours to obtain the cutting protection liquid.

[0109] Embodiment 14

[0110] Provided is a cutting protection liquid, comprising: 10 parts of a high molecular polymer, 63 parts of an organic solvent, 0.3 parts of a toughening agent, 0.001 parts of inorganic particles and 0.2 parts of an ultraviolet absorber;

[0111] Among them, the high molecular polymer is the high molecular polymer provided in Example 6, the organic solvent is methanol and methyl ethyl ether in a mass ratio of 20:1, the toughening agent is carboxyl nitrile rubber, the inorganic particles are nano calcium carbonate, and the ultraviolet absorber is phenyl o-hydroxybenzoate.

[0112] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 400 rpm for 2 hours to obtain the cutting protection liquid.

[0113] Embodiment 15

[0114] Provided is a cutting protection liquid, comprising: 25 parts of a high molecular polymer, 88 parts of an organic solvent, 1.6 parts of a toughening agent, 0.004 parts of inorganic particles and 0.3 parts of an ultraviolet absorber;

[0115] Among them, the high molecular polymer is the high molecular polymer provided in Example 7, the organic solvent is n-propanol and di-n-butyl ether in a mass ratio of 10:1, the toughening agent is chloroprene rubber, the inorganic particles are nano-silica, and the ultraviolet absorber is 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate sodium.

[0116] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 400 rpm for 2 hours to obtain the cutting protection liquid.

[0117] Example 16

[0118] Provided is a cutting protection liquid, comprising: 20 parts of a high molecular polymer, 75 parts of an organic solvent, 0.5 parts of a toughening agent, 0.005 parts of inorganic particles and 0.1 parts of an ultraviolet absorber;

[0119] The high molecular polymer is the high molecular polymer provided in Example 8, the organic solvent is isobutyl alcohol, the toughening agent is polysulfide rubber, the inorganic particles are nano-titanium dioxide, and the ultraviolet absorber is sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate.

[0120] The preparation method of the cutting protection liquid is as follows: weigh the above-mentioned high molecular polymer, organic solvent, toughening agent, inorganic particles and ultraviolet absorber in respective mass parts, and stir at a speed of 400 rpm for 2 hours to obtain the cutting protection liquid.

[0121] Comparative Example 1

[0122] A cutting protection liquid is provided, and the specific composition is similar to that of Example 9, except that the high molecular weight polymer of Example 1 is not used in Comparative Example 1, and polyvinyl pyrrolidone is used as a substitute.

[0123] Comparative Example 2

[0124] A cutting protection liquid is provided, and the specific composition is similar to that of Example 9, except that the toughening agent of Example 9 is not contained in Comparative Example 2.

[0125] Comparative Example 3

[0126] A cutting protection liquid is provided, and the specific composition is similar to that of Example 9, except that the inorganic particles of Example 9 are not contained in Comparative Example 3.

[0127] See also Figure 1-2 ,in, Figure 1 This is a microscope picture with a magnification of 500 times after coating with the cutting protection liquid of Example 9. Figure 2 The figure is a microscope picture with a magnification of 500 times after coating with the cutting protection liquid of comparative example 1. Figure 2 compared to, Figure 1 It can be seen that the chip is completely coated without any missing coating, which shows that Example 9 can simultaneously protect the bottom cutting path and step edge of the GaAs chip. Figure 2 It can be seen that the coating is incomplete and there are chips with missing coating, which means that Comparative Example 1 cannot simultaneously protect the cutting path and step edge at the bottom of the GaAs chip.

[0128] See also Figure 3 The ultraviolet spectrum of the cutting protection liquid of Example 9 shows that there is an obvious absorption peak at 350nm. The peak of the ultraviolet laser cutting machine is mainly around 355nm, and the cutting protection liquid of this example has an obvious absorption peak at 350nm, which can better absorb ultraviolet energy.

[0129] See Table 1 for a comparison of the coating effects of the cutting protection materials in Examples 9-16 and Comparative Examples 1-3. The coating effect test method is as follows: after obtaining the cutting protection liquid of each of the above-mentioned embodiments and comparative examples, 25 mL of the protection material is dripped onto the wafer, and then a spin coater is used to coat the wafer at a spin coating speed of 1000 rpm for 120 seconds to evenly coat the wafer and dry it into a film.

[0130] Table 1

[0131] Coating effect Example 9 Form a complete protective film Example 10 Form a complete protective film Embodiment 11 Form a complete protective film Example 12 Form a complete protective film Embodiment 13 Form a complete protective film Embodiment 14 Form a complete protective film Embodiment 15 Form a complete protective film Example 16 Form a complete protective film Comparative Example 1 Unable to form a complete protective film Comparative Example 2 Unable to form a complete protective film Comparative Example 3 Unable to form a complete protective film

[0132] It can be seen from Table 1 that compared with comparative examples 1-3, the cutting protection liquid of the present application has excellent film-forming properties, can adapt to substrates of different shapes, adhere to the surface of the substrate, form a complete protective film on the surface of the substrate, and has the characteristics of high adhesion. It has very good application prospects and large-scale industrial promotion potential in the field of chip cutting protection.

[0133] The above is a detailed introduction to a cutting protection liquid, a preparation method and an application thereof provided in the embodiments of the present application. Specific examples are used in the present application to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the technical scheme and core idea of ​​the present application. Ordinary technicians in this field should understand that they can still modify the technical schemes recorded in the aforementioned embodiments, or replace some of the technical features therein with equivalents; and these modifications or replacements do not make the essence of the corresponding technical scheme deviate from the scope of the technical schemes of the embodiments of the present application.

Claims

1. A cutting protection liquid, characterized in that: The composition comprises, by weight: 8 to 35 parts of a high molecular polymer, 50 to 100 parts of an organic solvent, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles and 0.1 to 0.5 parts of an ultraviolet absorber; The high molecular polymer comprises a first molecular chain bonded with an alkoxysilane, a second molecular chain bonded with a hydrophobic group and a third molecular chain bonded with a hydrophilic group; the high molecular polymer is prepared by mixing a reaction solvent, a first monomer, a second monomer and a third monomer, adding an initiator and reacting the mixture; the first monomer is selected from at least one of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltriisopropoxysilane; the second monomer is selected from at least one of methyl methacrylate, lauryl methacrylate, butyl methacrylate and octadecyl methacrylate; the third monomer is selected from at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate; The toughening agent is selected from at least one of polysulfide rubber, liquid silicone rubber, carboxyl nitrile rubber, chloroprene rubber, and acrylate rubber; The inorganic particles are selected from at least one of nano calcium carbonate, nano silicon dioxide and nano titanium dioxide.

2. The cutting protection liquid according to claim 1, characterized in that: The molecular weight of the high molecular weight polymer is 5000-50000; and / or The ultraviolet absorber is at least one selected from the group consisting of sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate, phenyl o-hydroxybenzoate, and o-nitroaniline; and / or The organic solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, ethyl ether, methyl ethyl ether, di-n-butyl ether, propylene glycol methyl ether, ethylene glycol propyl ether, ethyl acetate and n-butyl acetate.

3. The cutting protection liquid according to claim 2, characterized in that: The toughening agent is selected from acrylate rubber, the inorganic particles are selected from nano-calcium carbonate, and the mass ratio of the acrylate rubber to the nano-calcium carbonate is (100-500):1; and / or The organic solvent is selected from isopropyl alcohol and propylene glycol methyl ether, and the mass ratio of the isopropyl alcohol to the propylene glycol methyl ether is (1-20):

1.

4. A method for preparing the cutting protection liquid according to claim 1, characterized in that: The following steps are involved: Step 1: Mix a reaction solvent, a first monomer, a second monomer, and a third monomer, and then add an initiator to react to obtain a high molecular weight polymer; Step 2: Weigh 8 to 35 parts of a high molecular polymer, 0.1 to 2 parts of a toughening agent, 0.001 to 0.005 parts of inorganic particles, 0.1 to 0.5 parts of an ultraviolet absorber, and 50 to 100 parts of an organic solvent, respectively, mix and stir, and prepare a cutting protection liquid; The first monomer is selected from at least one of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane; The second monomer is selected from at least one of methyl methacrylate, lauryl methacrylate, butyl methacrylate, and octadecyl methacrylate; The third monomer is selected from at least one of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.

5. The method for preparing the cutting protection liquid according to claim 4, characterized in that: The molar ratio of the first monomer, the second monomer, the third monomer, the initiator and the reaction solvent is (1-5): (1-10): (1-5): (0.01-0.05): (15-20); In the step 1, the reaction temperature is 50-110°C and the reaction time is 6-8h; In the step 2, the stirring speed is 200-500 rpm and the stirring time is 1-5h.

6. Use of the cutting protection liquid according to any one of claims 1 to 3 in wafer cutting.

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