CN116875141A - Cutting protection material, preparation method and application thereof - Google Patents

Cutting protection material, preparation method and application thereof Download PDF

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Publication number
CN116875141A
CN116875141A CN202310755770.6A CN202310755770A CN116875141A CN 116875141 A CN116875141 A CN 116875141A CN 202310755770 A CN202310755770 A CN 202310755770A CN 116875141 A CN116875141 A CN 116875141A
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parts
water
protection material
soluble resin
structural unit
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侯军
褚雨露
马超男
张楠
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Jiangsu Austrian Mstar Technology Ltd
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Jiangsu Austrian Mstar Technology Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The application discloses a cutting protection material, a preparation method and application thereof, wherein the cutting protection material comprises the following components: 5 to 35 parts of water-soluble resin, 0.5 to 5 parts of plasticizer and 2 to 10 parts of organic solvent. The cutting protection material comprises water-soluble resin with pyrrolidone-based structural units and ester-based structural units, has excellent film forming property, can be suitable for substrates with different shapes and is attached to the surface of the substrate so as to form a complete protection film on the surface of the substrate; meanwhile, under the synergistic effect of the plasticizer, the flexibility of the film layer is increased, so that the cutting protection material is suitable for the three-dimensional structure of the complex chip.

Description

Cutting protection material, preparation method and application thereof
Technical Field
The application belongs to the technical field of chip cutting, and particularly relates to a cutting protection material, a preparation method and application thereof.
Background
In order to enrich the performance of GaAs-based chips, it is generally necessary to prepare a structure with a high aspect ratio, especially for GaAs-based chips containing copper pillars, since the height of the copper pillars protruding relative to the steps is large, the protection material used during laser cutting cannot protect the copper pillars, the step edges and the dicing streets between the steps at the same time, resulting in damage to the surfaces of the copper pillars during chip preparation.
Disclosure of Invention
Application purpose: the application provides a cutting protection material, a preparation method and application thereof, and aims to simultaneously protect a cutting channel at the bottom of a GaAs chip, the edge of a step and a Cu column on the step, and improve the yield and the productivity in the manufacturing process of a semiconductor.
The technical scheme is as follows: the application discloses a cutting protection material, which comprises the following components in parts by mass: 5 to 35 parts of water-soluble resin, 0.5 to 5 parts of plasticizer and 2 to 10 parts of organic solvent; the water-soluble resin has a first structural unit and a second structural unit, the first structural unit having a structure of the following formula (1):
the second structural unit has a structure of the following formula (2):
wherein R is 1 Selected from hydrogen or methyl; r is R 2 Selected from C 1 ～C 4 Alkyl, C of (2) 1 ～C 4 At least one of alkoxy, hydroxyethyl, hydroxypropyl.
In some embodiments, the water-soluble resin has a structural formula represented by the following formula (3):
wherein n represents the degree of polymerization of the first structural unit, and n is an integer from 10 to 200; m represents the polymerization degree of the second structural unit, and m is an integer of 20 to 300.
In some embodiments, the water-soluble resin further satisfies at least one of the following characteristics:
a) The molar ratio of the first structural unit to the second structural unit is (1-20): (2-30);
b)n：m＝(1～20)：(2～30)；
c) The molecular weight of the water-soluble resin is 10000-100000.
In some embodiments, the plasticizer is selected from at least one of glycerol, 1, 3-butanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600; 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.
In some embodiments, the cut protection material further comprises, in parts by mass: 1-6 parts of filler; wherein the filler is at least one selected from water-containing magnesium silicate, calcium carbonate, mica powder and water-containing nano silicon dioxide.
In some embodiments, the cut protection material further comprises, in parts by mass: 0.1 to 0.5 part of ultraviolet absorber, 0.1 to 1 part of corrosion inhibitor, 0.01 to 0.3 part of antibacterial agent and 35 to 80 parts of deionized water.
In some embodiments, the composition comprises, in parts by mass: 9 to 20 parts of water-soluble resin, 0.15 to 0.45 part of ultraviolet absorber, 0.2 to 0.8 part of corrosion inhibitor, 1 to 4 parts of plasticizer, 2 to 5 parts of filler, 0.05 to 0.2 part of antibacterial agent, 3 to 9 parts of organic solvent and 40 to 80 parts of deionized water.
In some embodiments, the ultraviolet absorber is selected from at least one of ferulic acid, 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-diethylamino-2-carboxybenzophenone; and/or
The corrosion inhibitor is at least one selected from cyclohexylamine, sodium silicate and sodium benzoate; and/or
The antibacterial agent is at least one selected from acetic acid, isothiazolinone, quaternary ammonium salts, phenols, inorganic silver, photocatalyst and zinc oxide whisker composite material.
In some embodiments, the present application also provides a method for preparing a cut protection material, comprising the steps of:
respectively weighing water-soluble resin, an ultraviolet absorber, a corrosion inhibitor, a plasticizer, a filler, an antibacterial agent, an organic solvent and deionized water in parts by mass, mixing and stirring to prepare a cutting protection material; wherein the stirring speed is 200-500 rpm; the stirring time is 1-5 h.
In some embodiments, the application also provides an application of the cutting protection material in laser cutting of chips.
The beneficial effects are that: compared with the prior art, the cutting protection material comprises the water-soluble resin with the pyrrolidone-based structural unit and the ester-based structural unit, the water-soluble resin has excellent film forming property, and can be suitable for substrates with different shapes and is attached to the surface of the substrate so as to form a complete protection film on the surface of the substrate; meanwhile, under the synergistic effect of the plasticizer, the flexibility of the film layer is increased, so that the cutting protection material is suitable for the three-dimensional structure of the complex chip.
It is understood that, compared with the prior art, the preparation method of the cutting protection material and the application of the cutting protection material provided by the embodiment of the application have all the technical features and beneficial effects of the composition, and are not repeated herein.
Drawings
The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.
FIG. 1 is a picture of an uncut chip;
FIG. 2 is a microscopic photograph at 650 times magnification of a chip cut coated with the cut protection material of example 1;
FIG. 3 is a microscope photograph at 650 times magnification after dicing of a chip coated with the dicing protective material of comparative example 1;
FIG. 4 is a microscope photograph at 650 times magnification of a chip coated with the comparative example 2 dicing protective material;
FIG. 5 is a microscope photograph at 650 times magnification after dicing of a chip coated with the dicing protective material of comparative example 3;
FIG. 6 is an infrared spectrum of the cut protection material prepared in example 1.
Detailed Description
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. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically connected, electrically connected or can be communicated with each other; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances. In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more features.
The following disclosure provides many different embodiments, or examples, for implementing different features of the application. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the application.
The applicant finds that a part of the product types of the three-generation semiconductor enterprises in China are GaAs-based chips, the chip structure of the GaAs-based chips is basically divided into two main types, one is that the surface of the chip is provided with a groove formed by etching, and a laser cutting channel is just arranged at the bottom of the groove; the other more complex is that the steps on two sides of the groove are provided with Cu columns, the width of the groove is unequal to 30-100 mu m, the height of the step is unequal to 10-20 mu m, and the height of the Cu columns is unequal to 60-80 mu m.
When the existing laser cutting protection material is used for a chip with a high aspect ratio structure, the problem that three positions of a bottom cutting channel, a step edge and a Cu column on a step cannot be protected simultaneously can occur. There is currently no very good solution for this type of chip laser protection material. Therefore, it is urgent to develop a laser cutting protection material capable of simultaneously protecting the bottom cutting channel, the step edge and the Cu post on the step of the GaAs chip.
Based on the above-mentioned problems, an embodiment of the present application provides a cutting protection material, including, in parts by mass: 5 to 35 parts of water-soluble resin, 0.5 to 5 parts of plasticizer and 2 to 10 parts of organic solvent; the water-soluble resin has a first structural unit and a second structural unit, the first structural unit having a structure of the following formula (1):
the second structural unit has the structure of the following formula (2):
wherein R is 1 Selected from the group consisting ofHydrogen or methyl; r is R 2 Selected from C 1 ～C 4 Alkyl, C of (2) 1 ～C 4 At least one of alkoxy, hydroxyethyl, hydroxypropyl.
It can be appreciated that the water-soluble resin comprises a structural unit containing a pyrrolidone group and a structural unit containing an ester group, and can be rapidly coated on the surface of a substrate with a complex structure to form a film so as to match different chip structures, in particular to match a complex chip structure containing a Cu column. In addition, the addition of the plasticizer can further generate a synergistic effect with the water-soluble resin to increase the flexibility of the film layer, so that the cutting protection material is suitable for the three-dimensional structure of the complex chip.
In some embodiments, the water-soluble resin has a structural formula represented by the following formula (3):
wherein n represents the degree of polymerization of the first structural unit, and n is an integer from 10 to 200; m represents the polymerization degree of the second structural unit, and m is an integer of 20 to 300.
Wherein when R is 1 When the polymer is methyl, the methyl can be further cooperated with the ester group to improve the adhesive force of the film layer; r is R 2 Preferably methyl, butyl, ethoxy and hydroxyethyl; still further preferred is hydroxyethyl, when R 2 When the hydroxyethyl group is adopted, the hydroxyl group at the tail end and the pyrrolidone group are cooperated to further improve the hydrophilicity, so that the integral film forming property of the water-soluble resin is improved, the water-soluble resin can be suitable for substrates with different shapes, the surfaces of the substrates are bonded, and a complete protective film is formed on the surfaces of the substrates.
It is understood that the water-soluble resin is a water-soluble pyrrolidone-ester copolymer resin and can be prepared by copolymerizing a first monomer and a second monomer, wherein the first monomer is vinyl pyrrolidone, and the second monomer is any one or more of methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate and ethoxyethoxyethyl acrylate.
Further, the water-soluble resin may be a linear structure, and the first monomer and the second monomer are randomly copolymerized. The water-soluble resin is a resin with hydrophilic groups introduced into side chains, and most preferably is a resin obtained by copolymerizing vinyl pyrrolidone and hydroxyethyl methacrylate; wherein, the preferable mass ratio of the vinyl pyrrolidone to the hydroxyethyl methacrylate is 6 (1-10), and the preferable mass ratio is 1:1.
Furthermore, the water-soluble resin can also have a body type structure, and because the vinyl pyrrolidone and the acrylic resin monomer with the hydrophilic group introduced into the side chain are adopted, the vinyl pyrrolidone and the acrylic resin monomer can form a net structure when being copolymerized, the strength and the elasticity of the resin are improved, the adhesive force of the resin is also enhanced, the vinyl pyrrolidone and the acrylic resin monomer can be firmly adsorbed on the surface of a substrate, and the substrate is protected.
In some embodiments, the water-soluble resin further satisfies: the molar ratio of the first structural unit to the second structural unit is (1-20): (2-30). For example, the molar ratio of the first structural unit to the second structural unit may be in a range between any one or any two of 1:1, 1:1.5, 1:5, 1:10.
In some embodiments, the water-soluble resin further satisfies: n: m= (1-20): (2-30). For example, n: m may be any one or a range between any two of 1:1, 1:1.5, 1:5, 1:10.
In some embodiments, the water-soluble resin has a molecular weight of 10000 to 100000; more preferably, the molecular weight of the water-soluble resin is 50000 to 80000.
In some embodiments, the plasticizer is selected from at least one of glycerol, 1, 3-butanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600. It can be understood that the plasticizer contains hydroxyl, has better compatibility with water-soluble resin, can further improve the water solubility of the resin, so as to reduce the defects of shrinkage cavity, orange peel and the like in the cutting process, and can also enhance the flexibility of the film layer, so that the film layer is suitable for a three-dimensional structure of a complex chip. It is further preferred that the plasticizer is 1, 3-butanediol, the 1, 3-butanediol is a polyhydroxy structure and is a small molecule, and has higher compatibility with the water-soluble resin than polyethylene glycol.
In some embodiments, the organic solvent is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, isobutanol, diethyl ether, methylethyl ether, di-n-butyl ether, propylene glycol methyl ether, ethylene glycol propyl ether, ethyl acetate, n-butyl acetate. The organic solvent is selected from any one or a combination of any plurality of alcohols, ethers and esters, and most preferably the organic solvent is ethanol and/or isopropanol.
In some embodiments, the cut protection material further comprises 1 to 6 parts of a filler; wherein the filler is at least one selected from water-containing magnesium silicate, calcium carbonate, mica powder and water-containing nano silicon dioxide. It can be understood that the filler can be fully and uniformly dispersed in the protective material, so that the film performance is comprehensively improved, the extensibility is improved, the liquid shrinkage is improved, and the bonding strength between the film and the surface of the chip is greatly improved. Further, the filler is preferably aqueous nanosilica because the aqueous nanosilica is nanoscale, has a smaller particle diameter, can be uniformly dispersed in the protective material, and acts together with the resin to form the protective film.
In some embodiments, the cut protection material further comprises 0.1 to 0.5 parts of an ultraviolet absorber, 0.1 to 1 part of a corrosion inhibitor, 0.01 to 0.3 part of an antimicrobial agent, and 35 to 80 parts of deionized water. It can be understood that the ultraviolet absorber is a light stabilizer, can absorb sunlight and ultraviolet rays in the fluorescent light source without change, and is used for effectively protecting the cutting protection material and weakening damage of ultraviolet rays to the cutting protection material; corrosion inhibitors are used to prevent or slow down the corrosion of materials; the antibacterial agent has a killing effect or growth inhibition effect on pathogenic microorganisms, and is a chemical substance for keeping the growth or propagation of certain microorganisms (bacteria, fungi, yeasts, algae, viruses, etc.) below a necessary level for a certain period of time.
In some embodiments, the ultraviolet absorber is selected from at least one of ferulic acid, 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-diethylamino-2-carboxybenzophenone.
In some embodiments, the corrosion inhibitor is selected from at least one of cyclohexylamine, sodium silicate, sodium benzoate.
In some embodiments, the antimicrobial agent is selected from at least one of acetic acid, isothiazolones, quaternary ammonium salts, phenols, inorganic silver-based, photo-catalysts, zinc oxide whisker composites.
In some embodiments, the cutting protection material preferably comprises, in parts by mass: 9 to 20 parts of water-soluble resin, 0.15 to 0.45 part of ultraviolet absorber, 0.2 to 0.8 part of corrosion inhibitor, 1 to 4 parts of plasticizer, 2 to 5 parts of filler, 0.05 to 0.2 part of antibacterial agent, 3 to 9 parts of organic solvent and 40 to 80 parts of deionized water.
In some embodiments, the method for preparing the water-soluble resin comprises the following specific steps: under the protection of nitrogen, adding the first monomer, the second monomer and the initiator into a reaction kettle, and heating and stirring to obtain the water-soluble resin.
Among them, the initiator may be azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, ammonium persulfate, etc., preferably azobisisobutyronitrile, benzoyl peroxide, most preferably azobisisobutyronitrile. The first monomer is vinyl pyrrolidone; the second monomer is at least one of methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate and ethoxyethoxyethyl acrylate. Preferably, the first monomer is vinyl pyrrolidone and the second monomer is hydroxyethyl methacrylate. The first monomer is used in an amount of 10 to 50 parts, preferably 20 to 40 parts, most preferably 20 to 30 parts; the second monomer is used in an amount of 10 to 60 parts, preferably 20 to 50 parts, most preferably 20 to 30 parts; the initiator is used in an amount of 0.2 to 1.5 parts, preferably 0.1 to 5 parts, most preferably 0.5 parts. The temperature of the heating and stirring is 50-110 ℃, preferably 75-85 ℃ and most preferably 80 ℃; the heating and stirring time is 2-48 hours, preferably 6-8 hours, and most preferably 7 hours.
In some embodiments, the method of preparing the cut protection material is as follows:
respectively weighing water-soluble resin, ultraviolet absorbent, corrosion inhibitor, plasticizer, filler, antibacterial agent, organic solvent and deionized water in parts by mass;
each component is added into a mixing container provided with a stirrer and stirred for 1 to 5 hours at the speed of 200 to 500rpm at the normal temperature, so as to obtain the cutting protection material.
Wherein, the stirring speed can be any one value or a range between any two values of 200rpm, 300rpm, 400rpm and 500rpm; the stirring time may be 1h, 2h, 3h, 4h or 5h.
In some embodiments, the method of using the cut protection material is as follows:
firstly, cleaning wafers with different sizes to be coated;
setting a spin coating program, and dripping a cutting protection material on wafer, wherein the dosage comprises: 10ml/4 inch, 15ml/6 inch, 25ml/8 inch, 35ml/12 inch, etc., spin-coated at 1000rpm for 2 minutes;
after spin coating, the next laser cutting process can be performed.
In some embodiments, the dicing protective material can be applied to laser dicing protection of chips, especially GaAs chips, and is suitable for various wafer structures, and a protective film is formed on the wafer surface to ensure that the chips are not scratched by fragments in the dicing process, especially the Cu pillars on the bottom dicing streets, step edges, and steps of the chips can be simultaneously protected, so as to improve the yield of semiconductor products and dicing efficiency. Therefore, the cutting protection material has very good application prospect and large-scale industrialized popularization potential in the field of chip laser cutting protection.
It can be understood that the cutting protection material provided in this embodiment can be well used in a laser cutting process of a chip, but considering the difference of specific components, the cutting protection material in this embodiment is not fully suitable for other cutting processes, such as diamond wire cutting, because the cutting action principle of different cutting processes is different, and the cutting protection material in this embodiment can solve the problem that the laser cutting requirements of different structures on the chip cannot be met at the same time under the action of the water-soluble resin with a specific structure, but these problems cannot occur in other cutting processes.
Example 1
There is provided a cut protection material comprising:
18 parts of water-soluble resin, 0.15 part of ultraviolet absorber, 0.5 part of corrosion inhibitor, 1 part of plasticizer, 2 parts of filler, 0.08 part of antibacterial agent, 9 parts of organic solvent and 70 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 80, m is 80; the ultraviolet absorbent is ferulic acid; the corrosion inhibitor is sodium benzoate; the plasticizer is 1, 3-butanediol; the filler is water-based nano silicon dioxide; the antibacterial agent is acetic acid; the organic solvent is ethanol.
The preparation method of the cutting protection material comprises the following steps: the water-soluble resin, the ultraviolet absorber, the corrosion inhibitor, the plasticizer, the filler, the antibacterial agent, the organic solvent and the deionized water which are respectively in parts by mass are weighed and stirred for 2 hours at the speed of 400rpm, so that the cutting protection material is obtained.
Example 2
There is provided a cut protection material comprising:
20 parts of water-soluble resin, 0.3 part of ultraviolet absorber, 0.8 part of corrosion inhibitor, 2 parts of plasticizer, 3 parts of filler, 0.2 part of antibacterial agent, 6 parts of organic solvent and 80 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 100, m is 150; the ultraviolet absorbent is 2-hydroxy-4-n-octoxybenzophenone; the corrosion inhibitor is cyclohexylamine; the plasticizer is glycerol; the filler is hydrous magnesium silicate; the antibacterial agent is isothiazolinone; the organic solvent is isopropanol.
The preparation method of the cutting protection material comprises the following steps: the water-soluble resin, the ultraviolet absorber, the corrosion inhibitor, the plasticizer, the filler, the antibacterial agent, the organic solvent and the deionized water which are respectively in parts by mass are weighed and stirred for 4 hours at the speed of 200rpm, so that the cutting protection material is obtained.
Example 3
There is provided a cut protection material comprising:
9 parts of water-soluble resin, 0.45 part of ultraviolet absorber, 0.3 part of corrosion inhibitor, 3 parts of plasticizer, 4 parts of filler, 0.15 part of antibacterial agent, 5 parts of organic solvent and 60 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 10, m is 50; the ultraviolet absorbent is 2, 4-dihydroxybenzophenone; the corrosion inhibitor is sodium silicate; the plasticizer is polyethylene glycol 400; the filler is calcium carbonate; the antibacterial agent is inorganic silver antibacterial agent MS-K004; the organic solvent is propylene glycol methyl ether.
The preparation method of the cutting protection material comprises the following steps: the water-soluble resin, the ultraviolet absorber, the corrosion inhibitor, the plasticizer, the filler, the antibacterial agent, the organic solvent and the deionized water which are respectively in parts by mass are weighed and stirred for 3 hours at the speed of 300rpm, so that the cutting protection material is obtained.
Example 4
There is provided a cut protection material comprising:
15 parts of water-soluble resin, 0.3 part of ultraviolet absorber, 0.4 part of corrosion inhibitor, 4 parts of plasticizer, 5 parts of filler, 0.05 part of antibacterial agent, 3 parts of organic solvent and 50 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 30, m is 300; the ultraviolet absorbent is 2-hydroxy-4-diethylamino-2-carboxyl diphenyl ketone; the corrosion inhibitor is sodium benzoate; the plasticizer is polyethylene glycol 600; the filler is mica powder; the antibacterial agent is a photocatalyst; the organic solvent is ethyl acetate.
The preparation method of the cutting protection material comprises the following steps: the water-soluble resin, the ultraviolet absorber, the corrosion inhibitor, the plasticizer, the filler, the antibacterial agent, the organic solvent and the deionized water which are respectively prepared by weight parts are weighed and stirred for 1h at the speed of 500rpm, so that the cutting protection material is obtained.
Example 5
There is provided a cut protection material comprising:
12 parts of water-soluble resin, 0.2 part of ultraviolet absorber, 0.2 part of corrosion inhibitor, 2 parts of plasticizer, 4 parts of filler, 0.1 part of antibacterial agent, 8 parts of organic solvent and 40 parts of deionized water.
Wherein the water-soluble resin has the structure ofn is 200, m is 200; the ultraviolet absorbent is 2-hydroxy-4-diethylamino-2-carboxyl diphenyl ketone; the corrosion inhibitor is sodium benzoate; the plasticizer is 1, 3-butanediol; the filler is water-based nano silicon dioxide; the antibacterial agent is zinc oxide whisker composite material; the organic solvent is ethanol.
The preparation method of the cutting protection material comprises the following steps: the water-soluble resin, the ultraviolet absorber, the corrosion inhibitor, the plasticizer, the filler, the antibacterial agent, the organic solvent and the deionized water which are respectively in parts by mass are weighed and stirred for 5 hours at the speed of 200rpm, so that the cutting protection material is obtained.
Example 6
There is provided a cut protection material comprising:
5 parts of water-soluble resin, 0.5 part of plasticizer, 10 parts of organic solvent and 50 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 10, m is 20; the plasticizer is 1, 3-butanediol; the organic solvent is ethanol.
The preparation method of the cutting protection material comprises the following steps: the respective parts by mass of the water-soluble resin, the plasticizer, the organic solvent and deionized water were weighed and stirred at a speed of 300rpm for 3 hours, thereby obtaining a cut protection material.
Example 7
There is provided a cut protection material comprising:
35 parts of water-soluble resin, 5 parts of plasticizer, 2 parts of organic solvent, 3 parts of filler and 70 parts of deionized water.
Wherein, the structure of the water-soluble resin is:n is 50, m is 50; plasticizer is 1,3-butanediol; the filler is water-based nano silicon dioxide; the organic solvent is ethanol.
The preparation method of the cutting protection material comprises the following steps: the respective parts by mass of the water-soluble resin, the plasticizer, the filler, the organic solvent and deionized water were weighed and stirred at a speed of 300rpm for 3 hours, thereby obtaining a cut protection material.
Comparative example 1
A cutting protection material is provided, the specific composition of which is similar to that of example 1, except that the water-soluble resin of example 1 is not used in comparative example 1, and polyvinylpyrrolidone is used instead.
Comparative example 2
A cut protection material is provided, the specific composition of which is similar to example 1, except that the plasticizer of example 1 is not contained in comparative example 1.
Comparative example 3
A cut protection material is provided having a specific composition similar to that of example 1, except that the filler of example 1 is not contained in comparative example 1.
1-5, wherein FIG. 1 is a photograph of an uncut chip, an uncut chip with high aspect ratio structure can be seen; FIG. 2 is a microscope photograph of the cut protection material of example 1 after it has been applied and cut and magnified 650 times; fig. 3, 4 and 5 are microscope pictures at 650 times magnified after coating the cut protection materials of comparative example 1, comparative example 2 and comparative example 3, respectively. Compared with the chip before dicing, it can be seen in fig. 2 that after dicing, dicing streets, copper pillars, steps are all protected; after dicing in fig. 3, the dicing streets burst and the dicing protective material of comparative example 1 did not protect the streets; the copper pillars on the chip after dicing in fig. 4 could not be protected by the dicing protective material of comparative example 2; the step after cutting in fig. 5 cannot be protected by the cutting protection material of example 3.
Further referring to FIG. 6, an infrared test chart of the water-soluble resin of example 1, which is visible on the infrared spectrum, 3359cm -1 Stretching vibration of hydroxyl at 2981cm -1 Stretching vibration of methyl at 1645cm -1 Characterised by the vinyl pyrrolidonePeaks, i.e., the telescopic vibration absorption peaks of carbonyl groups; 1453cm -1 And 1293cm -1 The C-H bending vibration absorption peak and the C-N stretching vibration absorption peak are respectively arranged at the positions. The water-soluble resin is polymerized by hydroxyethyl methacrylate and vinyl pyrrolidone.
See Table 1 for a comparison of the cutting performance properties of each of the cut protection materials of examples 1-7 and comparative examples 1-3. The cutting effect testing method comprises the following steps: after the laser cutting protective materials of the above respective examples and comparative examples were obtained, 25mL of the protective material was dropped onto wafer, and then coated on the wafer at a spin coating speed of 1000rpm using a spin coater for 120s, which was uniformly coated, dried to form a film, and then cut using a cutter.
TABLE 1
As can be seen from Table 1, compared with comparative examples 1-3, the cutting protection material of the application has excellent film forming property, can be suitable for substrates with different shapes, is attached to the surface of the substrate, forms a complete protection film on the surface of the substrate, has the characteristic of high adhesive force, and has very good application prospect and large-scale industrialized popularization potential in the field of chip laser cutting protection.
The cutting protection material, the preparation method and the application thereof provided by the embodiment of the application are described in detail, and the specific examples are applied to the application to explain the principle and the implementation mode of the application, and the description of the above embodiments is only used for helping to understand the technical scheme and the core idea of the application; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (10)

1. The cutting protection material is characterized by comprising the following components in parts by mass: 5 to 35 parts of water-soluble resin, 0.5 to 5 parts of plasticizer and 2 to 10 parts of organic solvent; the water-soluble resin has a first structural unit and a second structural unit, the first structural unit having a structure of the following formula (1):
the second structural unit has a structure of the following formula (2):
wherein R is 1 Selected from hydrogen or methyl; r is R 2 Selected from C 1 ～C 4 Alkyl, C of (2) 1 ～C 4 At least one of alkoxy, hydroxyethyl, hydroxypropyl.
2. The cutting protection material according to claim 1, wherein the structural formula of the water-soluble resin is represented by the following formula (3):
wherein n represents the degree of polymerization of the first structural unit, and n is an integer from 10 to 200; m represents the polymerization degree of the second structural unit, and m is an integer of 20 to 300.
3. The cut protection material of claim 2, wherein the water soluble resin further satisfies at least one of the following characteristics:
a) The molar ratio of the first structural unit to the second structural unit is (1-20): (2-30);
b)n：m＝(1～20)：(2～30)；
c) The molecular weight of the water-soluble resin is 10000-100000.
4. The cutting protection material of claim 1, wherein the plasticizer is selected from at least one of glycerol, 1, 3-butanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600; 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.
5. The cutting protection material according to claim 1, further comprising, in parts by mass: 1-6 parts of filler; wherein the filler is at least one selected from water-containing magnesium silicate, calcium carbonate, mica powder and water-containing nano silicon dioxide.
6. The cutting protection material according to claim 5, further comprising, in parts by mass: 0.1 to 0.5 part of ultraviolet absorber, 0.1 to 1 part of corrosion inhibitor, 0.01 to 0.3 part of antibacterial agent and 35 to 80 parts of deionized water.
7. The cutting protection material according to claim 6, comprising, in parts by mass: 9 to 20 parts of water-soluble resin, 0.15 to 0.45 part of ultraviolet absorber, 0.2 to 0.8 part of corrosion inhibitor, 1 to 4 parts of plasticizer, 2 to 5 parts of filler, 0.05 to 0.2 part of antibacterial agent, 3 to 9 parts of organic solvent and 40 to 80 parts of deionized water.
8. The cutting protective material according to claim 6, wherein the ultraviolet absorber is at least one selected from the group consisting of ferulic acid, 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-diethylamino-2-carboxybenzophenone; and/or
The corrosion inhibitor is at least one selected from cyclohexylamine, sodium silicate and sodium benzoate; and/or
The antibacterial agent is at least one selected from acetic acid, isothiazolinone, quaternary ammonium salts, phenols, inorganic silver, photocatalyst and zinc oxide whisker composite material.
9. A method of producing a cut protection material according to any one of claims 1 to 8, comprising the steps of:
respectively weighing water-soluble resin, an ultraviolet absorber, a corrosion inhibitor, a plasticizer, a filler, an antibacterial agent, an organic solvent and deionized water in parts by mass, mixing and stirring to prepare a cutting protection material; wherein the stirring speed is 200-500 rpm; the stirring time is 1-5 h.
10. Use of a dicing protective material according to any one of claims 1-8 in laser dicing of chips.
CN202310755770.6A 2023-06-26 2023-06-26 Cutting protection material, preparation method and application thereof Pending CN116875141A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104231503A (en) * 2014-08-15 2014-12-24 深圳市容大感光科技股份有限公司 Water-soluble resin composition
CN104449428A (en) * 2014-12-24 2015-03-25 湖北固润科技股份有限公司 Water-based photo-cured binder for cutting glass
CN106565895A (en) * 2016-10-26 2017-04-19 上海维凯光电新材料有限公司 Alcohol-soluble high-adhesive force acrylic resin and preparation method thereof
JP2020066667A (en) * 2018-10-23 2020-04-30 日本酢ビ・ポバール株式会社 Protective film-forming composition
CN116004072A (en) * 2022-12-26 2023-04-25 浙江奥首材料科技有限公司 Composition, preparation method and application thereof in wafer laser cutting

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104231503A (en) * 2014-08-15 2014-12-24 深圳市容大感光科技股份有限公司 Water-soluble resin composition
CN104449428A (en) * 2014-12-24 2015-03-25 湖北固润科技股份有限公司 Water-based photo-cured binder for cutting glass
CN106565895A (en) * 2016-10-26 2017-04-19 上海维凯光电新材料有限公司 Alcohol-soluble high-adhesive force acrylic resin and preparation method thereof
JP2020066667A (en) * 2018-10-23 2020-04-30 日本酢ビ・ポバール株式会社 Protective film-forming composition
CN116004072A (en) * 2022-12-26 2023-04-25 浙江奥首材料科技有限公司 Composition, preparation method and application thereof in wafer laser cutting

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