CN116987426A - Cutting protection liquid, preparation method and application thereof - Google Patents

Abstract

This application discloses a cutting protection liquid, its preparation method and application. The cutting protection liquid includes a high molecular polymer and an organic solvent; the high molecular polymer has a first molecular chain bonded with an alkoxysilane, a hydrophobic bonded The second molecular chain of the group and the third molecular chain bonded with the hydrophilic group, the first molecular chain, the second molecular chain and the third molecular chain are connected in sequence. The cutting protective fluid can be adapted to substrates of different shapes, adhere to the surface of the substrate, and form a complete protective film on the surface of the substrate; moreover, the protective film is alkali sensitive, and after the cutting process is completed, the protective film can be alkali-resistant Sexual solvents are completely removed and the cleaning process is simple.

Description

A kind of cutting protection liquid, its preparation method and application

Technical field

The present application belongs to the field of chip cutting technology, and specifically relates to a cutting protection liquid, its preparation method and application.

Background technique

GaAs-based chips generally have high aspect ratio structures. When laser cutting protective fluid is used on chips with high aspect ratio structures, there will be problems such as the bottom cutting lane bursting or the step edge being unable to protect the slag residue. Therefore, it is necessary to develop a method that can simultaneously Laser cutting protective fluid to protect the bottom cutting lane and step edges of GaAs chips.

Contents of the invention

Purpose of application: This application provides a cutting protection liquid, its preparation method and application, aiming to simultaneously protect the bottom cutting lane and step edges of GaAs chips, and improve the yield rate and productivity in the semiconductor manufacturing process.

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 and a second molecular chain bonded with a hydrophobic group. The molecular chain and the third molecular chain bonded with a hydrophilic group, the first molecular chain, the second molecular chain and the third molecular chain are connected in sequence.

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

The hydrophobic group is selected from at least one of methyl and ethyl; and/or

The hydrophilic group is selected from at least one of ester group, carboxyl group and hydroxyl group.

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.

In some embodiments, it includes: 8 to 35 parts of high molecular polymer, 50 to 100 parts of organic solvent, 0.1 to 2 parts of toughening agent, 0.001 to 0.005 parts of inorganic particles and 0.1 to 0.005 parts of inorganic particles. 0.5 parts of UV absorber.

In some embodiments, the molecular weight of the high molecular polymer is 5,000 to 50,000; and/or

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

The inorganic particles are selected from at least one of nanometer calcium carbonate, nanometer silica, and nanometer titanium dioxide; and/or

The ultraviolet absorber is selected from at least 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-sodium disulfonate, phenyl o-hydroxybenzoate, and o-nitroaniline. a; and/or

The organic solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, diethyl ether, methyl ethyl ether, di-n-butyl ether, propylene glycol methyl ether, and ethylene glycol. At least one of propyl ether, ethyl acetate, and n-butyl acetate.

In some embodiments, the toughening agent is selected from acrylate rubber, the inorganic particles are selected from nanometer calcium carbonate, and the mass ratio of the acrylate rubber to the nanometer 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.

In some embodiments, this application also provides a method for preparing a cutting protection liquid, including the following steps:

Step 1: Mix the reaction solvent, the first monomer, the second monomer, and the third monomer, then add the initiator, and react to obtain a polymer;

Step 2: Weigh 8 to 35 parts of high molecular polymer, 0.1 to 2 parts of toughening agent, 0.001 to 0.005 parts of inorganic particles, 0.1 to 0.5 parts of ultraviolet absorber and 50 to 100 parts of organic solvent. After mixing and stirring, a cutting protection liquid is prepared.

In some embodiments, the first monomer is selected from γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane At least one of the silanes;

The second monomer is selected from at least one of methyl methacrylate, lauryl methacrylate, butyl methacrylate, and stearyl methacrylate;

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

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);

In the step one, the reaction temperature is 50-110°C, and the reaction time is 6-8h;

In the second step, the stirring speed is 200-500rpm, and the stirring time is 1-5h.

In some embodiments, this application also provides the application of the cutting protection liquid in wafer cutting.

Beneficial effects: Compared with the prior art, the cutting protection solution of the present application includes a first molecular chain with an alkoxysilane, a second molecular chain with a hydrophobic group, and a third molecular chain with a hydrophilic group, wherein , the alkoxysilane improves the adhesion of the cutting protection fluid, the hydrophobic group improves the water resistance of the cutting protection fluid, and the hydrophilic group improves the film-forming property of the cutting protection fluid. The cutting protection fluid can be adapted to different shapes. The base material adheres to the surface of the base material to form a complete protective film on the surface of the base material; 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.

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 by the embodiments of the present application have all the technical features and beneficial effects of the above composition, and will not be described again here.

Description of drawings

The technical solutions and other beneficial effects of the present application will be apparent through a detailed description of the specific embodiments of the present application in conjunction with the accompanying drawings.

Figure 1 is a microscope picture with a magnification of 500 times after being coated with the cutting protection liquid of Example 9;

Figure 2 is a microscope picture with a magnification of 500 times after being coated with the cutting protection liquid of Comparative Example 1;

Figure 3 is the ultraviolet spectrum of the cutting protection liquid of Example 9.

Detailed ways

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts fall within the scope of protection of this application.

In the description of this application, it should be noted that, unless otherwise clearly stated 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. Ground connection; it can be a mechanical connection, an electrical connection, or mutual communication; it can be a direct connection, or an indirect connection through an intermediate medium, or an internal connection between two components or an interaction between two components. For those of ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances. In the description of this application, "plurality" means two or more than two, unless otherwise explicitly and specifically limited. 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 quantity of indicated technical features. Therefore, the features defined as “first” and “second” may explicitly or implicitly include one or more features.

The following disclosure provides many different embodiments or examples for implementing the various structures of the present application. To simplify the disclosure of the present application, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the application.

The applicant found that part of the product types of domestic third-generation semiconductor companies are GaAs-based chips, and the chip structures generally have high aspect ratio structures. Commonly, there is a layer of steps on the cutting track, with the width of the cutting track ranging from 25-65μm and the height of the step ranging from 9-20μm. When laser cutting protective fluid is used on chips with a high aspect ratio structure, there will be problems such as the bottom cutting track bursting or the step edge being unprotected and slag remaining. 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 lane and step edges of GaAs chips.

Embodiments of the present application provide a cutting protection liquid, including a high molecular polymer and an organic solvent; the high molecular polymer has a first molecular chain bonded with an alkoxysilane and 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.

It can be understood that the cutting protection fluid of the present application is adaptable to substrates of different shapes, fits 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 polymer contains alkoxysilane, hydrophobic groups and hydrophilic groups at the same time; among them, alkoxysilane improves the adhesion of the polymer to the substrate through molecular bridges. And alkoxysilane can react with polymers to combine alkoxysilane groups to the polymer main chain, and then react with water vapor to achieve cross-linking and form a stable three-dimensional structure. Due to the formation of a network structure after polymerization , can also improve the strength and elasticity of the polymer, and enhance the adhesion of the polymer, which can firmly protect the substrate; the hydrophobic group can form a hydrophobic layer on the surface of the cutting fluid to prevent the cutting fluid from being absorbed during cutting. Water dissolves; the hydrophilic group in the cutting fluid improves the flexibility of the polymer, promotes the polymer to form a film on the surface of the substrate, makes the film softer, and enhances the coating force.

Furthermore, the cutting protection fluid can be adapted 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 fluid is coated on the chip surface, the protective film formed is alkali-sensitive. After the cutting process is completed, the protective film can be completely removed by alkaline solvents, and the cleaning process is simple.

In some embodiments, the alkoxysilane is selected from at least one of methoxysilane, ethoxysilane, and propoxysilane. It can be understood that the silanes with hydrophobic organic groups on the silicon atoms of the above-mentioned alkoxysilane can further cooperate with other hydrophobic groups to impart hydrophobic properties to the surface of the cutting fluid.

In some embodiments, the hydrophobic group is selected from at least one of methyl and ethyl. Methyl is preferred.

In some embodiments, the hydrophilic group is selected from at least one of ester group, carboxyl group, and hydroxyl group. An ester group is preferred.

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. Wherein, the first molecular chain is selected from the structural units of olefins. For example, the monomer corresponding to the first molecular chain can be γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyl triisopropoxysilane; the second molecular chain is selected from the structural units of acrylic acid. For example, the monomer corresponding to the second molecular chain can be methyl methacrylate, lauryl methacrylate, methacrylate, etc. butyl acrylate, stearyl methacrylate; the third molecular chain is selected from the structural units of acrylic acid. For example, the monomer corresponding to the third molecular chain can be ethyl acrylate, butyl acrylate, or 2-ethyl acrylate. Hexyl acrylate, lauryl acrylate.

Furthermore, in addition to hydrophobic groups, the second molecular chain can also be connected with hydrophilic groups, such as ester groups; by connecting other hydrophilic groups to the second molecular chain, polymer polymerization can be further improved. The flexibility of the material improves the adhesion of the cutting protective fluid to form a film on the surface of the substrate.

Further, in parts by mass, the cutting protection liquid includes: 8 to 35 parts of high molecular polymer, 50 to 100 parts of organic solvent, 0.1 to 2 parts of toughening agent, 0.001 to 0.005 parts of Inorganic particles and 0.1 to 0.5 parts of ultraviolet absorber.

In some embodiments, in parts by mass, the cutting protection liquid includes: 12 to 18 parts of high molecular polymer, 70 to 85 parts of organic solvent, 0.5 to 1.5 parts of toughening agent, and 0.002 to 0.003 parts of inorganic particles. and 0.2 to 0.4 parts of UV absorber.

In some embodiments, the molecular weight of the high molecular polymer ranges from 5,000 to 50,000. Preferably it is 20000-30000. The polymerization conditions are controlled so that the molecular weight of the polymer ranges from 20,000 to 30,000. Within this molecular weight range, the polymer has excellent film-forming properties and can be adapted to substrates of different shapes.

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 being miscible with the polymer, the active groups in the toughening agent can participate in curing and improve the overall elongation at break and impact strength. The preferred toughening agent is acrylic rubber. This is because acrylic rubber and high molecular polymers belong to the acrylic series. They have high compatibility and can further increase the flexibility of the film layer, allowing the film layer to better follow the substrate. The complex structure and soft coating reduce its brittleness and prevent the film from breaking.

In some embodiments, in order to further improve the dispersion effect of the toughening agent in the polymer, the cutting protection liquid also includes inorganic particles, and the inorganic particles are selected from nanometer calcium carbonate, nanometer silica, and nanometer titanium dioxide. At least one; among them, the preferred inorganic particles are nano-calcium carbonate. This is because nano-calcium carbonate is nanoscale and has a smaller particle size. It can be evenly dispersed in the protective liquid and interact with high molecular polymers to form protective membrane.

In some embodiments, the UV absorber is selected from sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate, phenyl o-hydroxybenzoate, o-nitro At least one kind of aniline; UV absorber is a kind of light stabilizer, which can absorb the ultraviolet part of sunlight and fluorescent light sources without changing itself. Use ultraviolet absorber to effectively protect cutting protection materials and weaken ultraviolet rays. its destruction. The preferred ultraviolet absorber is sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate with two benzene rings, which has two conjugated benzene rings. It has extremely high solubility in the mixed solvent of propylene glycol methyl ether and isopropyl alcohol, good compatibility with polymers, and can be evenly dispersed in the material. After being formulated into a protective solution, it has an obvious absorption peak at 350nm, and the cutting effect is better. And it has good chemical stability and does not react adversely with material components.

In some embodiments, the organic solvent is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, diethyl ether, methyl ethyl ether, di-n-butyl ether, propylene glycol methyl ether , at least one of ethylene glycol propyl ether, ethyl acetate, and n-butyl acetate. The organic solvent is preferably a combination of isopropyl alcohol and propylene glycol methyl ether. The flash point of isopropyl alcohol is 11.7°C. It is easy to volatilize and dry quickly to form a film. The propylene glycol methyl ether molecule contains both alcohol and ether functional groups, which can provide unique polarity and non-toxic properties. Polar solubility and good compatibility with isopropyl alcohol. Among them, the mass ratio of isopropyl alcohol and propylene glycol methyl ether is (1-20):1. For example, the mass ratio of isopropyl alcohol and propylene glycol methyl ether can be 1:1, 2:1, 5:1, 8:1 , any ratio among 10:1, 12:1, 15:1, 18:1, 20:1 or the range between any two ratios.

In some embodiments, the toughening agent is selected from acrylate rubber, the inorganic particles are selected from nanometer calcium carbonate, and the mass ratio of acrylate rubber to nanometer calcium carbonate is (100-500):1, for example, acrylate rubber and nanometer calcium carbonate The mass ratio of calcium carbonate can be any ratio among 100:1, 200:1, 300:1, 400:1, 500:1 or the range between any two ratios.

The embodiment of the present application also provides a method for preparing a cutting protection liquid, which includes the following steps:

Step 1: Mix the reaction solvent, the first monomer, the second monomer, and the third monomer, then add the initiator, and react to obtain a polymer;

Step 2: Weigh 8 to 35 parts of high molecular polymer, 0.1 to 2 parts of toughening agent, 0.001 to 0.005 parts of inorganic particles, 0.1 to 0.5 parts of ultraviolet absorber and 50 to 100 parts of organic solvent. After mixing and stirring, a cutting protection liquid is prepared.

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 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C Any one value in or the range between any two values; the reaction time is any one value in 6h, 7h, 8h or the range between any two values.

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 value among 1h, 2h, 3h, 4h, 5h or the range between any two values.

In some embodiments, the first monomer is selected from gamma-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane at least one of them.

In some embodiments, the high molecular polymer is preferably prepared by copolymerization of methyl methacrylate, ethyl acrylate, and γ-methacryloyloxypropyltrimethoxysilane.

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

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

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).

In some embodiments, the initiator can be azobisisobutyronitrile, azobisisoheptanitrile, benzoyl peroxide, ammonium persulfate, etc., preferably azobisisobutyronitrile, benzoyl peroxide, Most preferred is azobisisobutyronitrile.

In some embodiments, the preparation method of the cutting protection liquid specifically includes:

Weigh the respective mass parts of polymer, toughener, ultraviolet absorber, inorganic particles and organic solvent;

Add each component into a mixing container equipped with a mixer, and stir at room temperature at a speed of 200 to 500 rpm for 1 to 5 hours to obtain a cutting protection liquid. The normal temperature here specifically refers to 25°C.

In some embodiments, the embodiments of the present application also provide methods for using cutting protection liquid, specifically as follows:

First clean the chips of different sizes to be coated;

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

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

In some embodiments, the cutting protection liquid can be used to protect chips, especially GaAs chips, and can protect the bottom cutting lanes and step edges of GaAs chips at the same time; it can be adapted to various wafer structures and form a protective film on the surface of the wafer. Ensure that the wafer is not scratched by debris during the cutting process to improve the yield of semiconductor products and cutting efficiency. Therefore, the cutting protection fluid of the present application has very good application prospects and large-scale industrial promotion potential in the field of semiconductor cutting protection.

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

Example 1

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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-methacryloyloxy Propyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisobutyronitrile.

Example 2

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 50°C for 8 hours to obtain a high molecular polymer. Among them, 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 vinyltrimethoxysilane, and the The second monomer is butyl methacrylate, the third monomer is butyl acrylate, and the initiator is azobisisoheptanitrile.

Example 3

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 110°C for 6 hours to obtain a high molecular polymer. Among them, 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 vinyltriethoxysilane, The second monomer is lauryl methacrylate, the third monomer is lauryl acrylate, and the initiator is benzoyl peroxide.

Example 4

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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 triisopropoxysilane , the second monomer is stearyl methacrylate, the third monomer is 2-ethylhexyl acrylate, and the initiator is ammonium persulfate.

Example 5

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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-methacryloyloxy Propyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisoheptanitrile.

Example 6

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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-methacryloyloxy Propyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is benzoyl peroxide.

Example 7

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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-methacryloyloxy Propyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is ammonium persulfate.

Example 8

A high molecular polymer is provided. The specific preparation process is as follows: 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. , stirred and reacted at 80°C for 7 hours to obtain a high molecular polymer. Among them, 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-methacryloyloxy Propyltrimethoxysilane, the second monomer is methyl methacrylate, the third monomer is ethyl acrylate, and the initiator is azobisisoheptanitrile.

Example 9

A cutting protection fluid is provided, including: 15 parts of high molecular polymer, 80 parts of organic solvent, 1 part of toughening agent, 0.005 parts of inorganic particles and 0.3 parts of ultraviolet absorber;

Wherein, the high molecular polymer is the high molecular polymer provided in Example 1, the organic solvent is isopropyl alcohol and propylene glycol methyl ether with a mass ratio of 4:1, the toughening agent is acrylate rubber, and the inorganic particles are nanometer calcium carbonate. The ultraviolet absorber is sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate.

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

Example 10

A cutting protection fluid is provided, including: 12 parts of high molecular polymer, 70 parts of organic solvent, 0.5 part of toughening agent, 0.005 part of inorganic particles and 0.2 part of ultraviolet absorber;

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 with a mass ratio of 1:1, the toughening agent is carboxyl liquid nitrile rubber, and the inorganic particles are nano dielectric Silicon oxide, UV absorber is phenyl ortho-hydroxybenzoate.

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

Example 11

A cutting protection fluid is provided, including: 18 parts of high molecular polymer, 85 parts of organic solvent, 1.5 parts of toughening agent, 0.005 parts of inorganic particles and 0.4 parts of ultraviolet absorber;

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 with a mass ratio of 16:1, the toughening agent is carboxyl-terminated liquid nitrile rubber, and the inorganic particles are nanometer Titanium dioxide, UV absorber is o-nitroaniline.

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

Example 12

A cutting protection fluid is provided, including: 8 parts of high molecular polymer, 50 parts of organic solvent, 0.1 part of toughening agent, 0.001 part of inorganic particles and 0.1 part of ultraviolet absorber;

Wherein, the high molecular polymer is the high molecular polymer provided in Example 4, the organic solvent is ethanol and ethylene glycol propyl ether with a mass ratio of 4:1, the toughening agent is polysulfide rubber, and the inorganic particles are nanometer calcium carbonate. The UV absorber is phenyl ortho-hydroxybenzoate.

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

Example 13

A cutting protection fluid is provided, including: 35 parts of high molecular polymer, 100 parts of organic solvent, 2 parts of toughening agent, 0.004 parts of inorganic particles and 0.5 parts of ultraviolet absorber;

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

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

Example 14

A cutting protection fluid is provided, including: 10 parts of high molecular polymer, 63 parts of organic solvent, 0.3 part of toughening agent, 0.001 part of inorganic particles and 0.2 part of ultraviolet absorber;

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

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

Example 15

A cutting protection fluid is provided, including: 25 parts of high molecular polymer, 88 parts of organic solvent, 1.6 parts of toughening agent, 0.004 parts of inorganic particles and 0.3 parts of ultraviolet absorber;

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 with a mass ratio of 10:1, the toughening agent is chloroprene rubber, and the inorganic particles are nanometer dioxide. Silicon, UV absorber is sodium 2,2-dihydroxy-4,4-dimethoxybenzophenone-5,5-disulfonate.

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

Example 16

A cutting protection fluid is provided, including: 20 parts of high molecular polymer, 75 parts of organic solvent, 0.5 part of toughening agent, 0.005 part of inorganic particles and 0.1 part of ultraviolet absorber;

Among them, the high molecular polymer is the high molecular polymer provided in Example 8, the organic solvent is isobutanol, the toughening agent is polysulfide rubber, the inorganic particles are nano titanium dioxide, and the ultraviolet absorber is 2,2-dihydroxy-4 , Sodium 4-dimethoxybenzophenone-5,5-disulfonate.

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

Comparative example 1

A cutting protection liquid is provided. The specific composition is similar to that of Example 9. The difference is that in Comparative Example 1, the polymer of Example 1 is not used and polyvinylpyrrolidone is used instead.

Comparative example 2

A cutting protection liquid is provided. The specific composition is similar to that of Example 9. The difference is that Comparative Example 2 does not contain the toughening agent of Example 9.

Comparative example 3

A cutting protection liquid is provided. The specific composition is similar to that of Example 9. The difference is that Comparative Example 3 does not contain the inorganic particles of Example 9.

Refer to Figures 1-2. Figure 1 is a microscope picture with a magnification of 500 times after being coated with the cutting protection liquid of Example 9. Figure 2 is a microscope picture with a magnification of 500 times after being coated with the cutting protection liquid of Comparative Example 1. . Compared with Figure 2, in Figure 1 you can see that the coating is complete and there are no coating leaks, indicating that Embodiment 9 can protect the bottom cutting line and step edge of the GaAs chip at the same time. In Figure 2, you can see that the coating is incomplete and there are no coating leaks. The coated chip shows that Comparative Example 1 cannot protect the bottom cutting lane and step edge of the GaAs chip at the same time.

Further referring to Figure 3, which is the ultraviolet spectrum of the cutting protection liquid of Example 9, it can be seen that there is an obvious absorption peak exactly at 350nm. The peak section of the ultraviolet laser cutting machine is mainly around 355nm, while the cutting protection liquid of this embodiment is exactly at 350nm. There is an obvious absorption peak, which can better absorb ultraviolet energy.

See Table 1 for a comparison of the coating effects and performance of each cutting protection material in Examples 9-16 and Comparative Examples 1-3. Among them, the coating effect test method is: after obtaining the cutting protection liquid of each of the above embodiments and comparative examples, drop 25 mL of protective material onto the wafer, and then use a spin coater to coat the wafer at a spin coating speed of 1000 rpm. On the above wafer, the coating time is 120s to make it evenly coated and dried to form a film.

Table 1

Coating effect Example 9 Form a complete protective film Example 10 Form a complete protective film Example 11 Form a complete protective film Example 12 Form a complete protective film Example 13 Form a complete protective film Example 14 Form a complete protective film Example 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

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

The above is a detailed introduction to a cutting protection liquid, its preparation method and application provided in the embodiments of the present application. Specific examples are used in this application to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only for use. To help understand the technical solutions and core ideas of the present application; those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent substitutions for some of the technical features; and these Modification or replacement does not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of each embodiment of the present application.

Claims (10)

1. The cutting protection liquid is characterized by comprising a high molecular polymer and an organic solvent; the high-molecular polymer is provided with a first molecular chain bonded with alkoxy silane, a second molecular chain bonded with hydrophobic group and a third molecular chain bonded with hydrophilic group, and the first molecular chain, the second molecular chain and the third molecular chain are sequentially connected.

2. The cutting protection fluid of claim 1, wherein the alkoxysilane is selected from at least one of methoxy silane, ethoxy silane, and propoxy silane; and/or

The hydrophobic group is at least one selected from methyl and ethyl; and/or

The hydrophilic group is at least one selected from ester group, carboxyl group and hydroxyl group.

3. The cleavage protection liquid according to claim 1, characterized in that the first molecular chain is selected from the group of structural units of olefins; the second molecular chain is selected from structural units of acrylic acid; the third molecular chain is selected from structural units of acrylic acid.

4. The cutting protection liquid according to claim 1, comprising, in parts by mass: 8 to 35 parts of high molecular polymer, 50 to 100 parts of organic solvent, 0.1 to 2 parts of toughening agent, 0.001 to 0.005 part of inorganic particles and 0.1 to 0.5 part of ultraviolet absorber.

5. The cutting protection fluid according to claim 4, wherein the molecular weight of the high molecular polymer is 5000-50000; and/or

The toughening agent is 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

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

The ultraviolet absorbent is selected from at least one of 2, 2-dihydroxyl-4, 4-dimethoxy benzophenone-5, 5-disulfonate, phenyl o-hydroxybenzoate and o-nitroaniline; and/or

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

6. The cutting protection fluid according to claim 5, wherein 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.

7. The preparation method of the cutting protection liquid is characterized by comprising the following steps of:

step one, mixing a reaction solvent, a first monomer, a second monomer and a third monomer, adding an initiator, and reacting to obtain a high-molecular polymer;

and step two, respectively weighing 8-35 parts of high molecular polymer, 0.1-2 parts of toughening agent, 0.001-0.005 part of inorganic particles, 0.1-0.5 part of ultraviolet absorber and 50-100 parts of organic solvent, mixing and stirring to prepare the cutting protection liquid.

8. The method for preparing a cutting protection fluid according to claim 7, wherein the first monomer is at least one selected from the group consisting of gamma-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane, vinyl triisopropoxysilane;

the second monomer is at least one selected from methyl methacrylate, lauryl methacrylate, butyl methacrylate and stearyl methacrylate;

the third monomer is at least one selected from ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl acrylate.

9. The method for producing a cutting protection fluid according to claim 7, wherein 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;

in the first step, the reaction temperature is 50-110 ℃ and the reaction time is 6-8h;

in the second step, the stirring speed is 200-500rpm, and the stirring time is 1-5h.

10. Use of a cleavage protecting liquid according to any one of claims 1-7 in wafer cleavage.