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CN115895356B - Protective material for silicon wafer cutting and preparation method thereof - Google Patents

Protective material for silicon wafer cutting and preparation method thereof Download PDF

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CN115895356B
CN115895356B CN202211474781.9A CN202211474781A CN115895356B CN 115895356 B CN115895356 B CN 115895356B CN 202211474781 A CN202211474781 A CN 202211474781A CN 115895356 B CN115895356 B CN 115895356B
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water
silicon wafer
wafer cutting
protective material
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CN115895356A (en
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吴娜娜
邓联文
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KUNSHAN HANPIN ELECTRONICS CO Ltd
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Hanping Kunshan Electronic Co ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention provides a protective material for silicon wafer cutting and a preparation method thereof, and relates to the technical field of wafer cutting protection. The protective material for silicon wafer cutting comprises the following raw materials in parts by weight: 30-40 parts of water-soluble resin, 0.5-1 part of carbon nano tube, 7-12 parts of aromatic carboxylic anhydride, 3-8 parts of long-chain polyunsaturated fatty acid, 0.2-1 part of wetting agent, 0.1-1 part of defoamer, 10-20 parts of organic solvent and 40-60 parts of water. The protective material for silicon wafer cutting can rapidly form a film on the surface of a wafer, has high strength after film formation, has good heat resistance, can effectively prevent condensed silicon vapor or other scraps generated in the processing process from being deposited on the surface of a chip during wafer processing, improves the quality and reliability of products, and has good film removing property.

Description

Protective material for silicon wafer cutting and preparation method thereof
Technical Field
The invention relates to the technical field of wafer cutting protection, in particular to a protective material for silicon wafer cutting and a preparation method thereof.
Background
Wafer refers to a silicon wafer used in the manufacture of a silicon semiconductor integrated circuit, and wafer dicing is a key process in the packaging process of the integrated circuit, and mainly, the whole wafer is divided into single chips according to the size of the chips by external force.
With the development and progress of technology, the current wafer dicing has been changed from the original simple blade dicing to the laser dicing, and the contact dicing is improved to the non-contact dicing. The laser cutting can greatly reduce the mechanical and stress damage to the chip in the cutting process, improves the product yield, and has become the mainstream in the current wafer cutting. Most of semiconductor chips are silicon chips, silicon is a brittle material, the strength of the chips can be influenced by corner fracture, the surface smoothness can be easily damaged in the cutting process, the pollution can be caused to the subsequent process, and in order to avoid the problems, a layer of protective film is required to be arranged in the wafer cutting process, so that a certain protective effect is achieved, and the subsequent trouble is avoided.
Researchers find that most of the wafer dicing protective solutions in the market can improve the dicing efficiency and stability of the wafer to a certain extent and avoid the problem of chipping or cracking and thermal stress, but many of the heat resistance in the protective solutions are not ideal, so that the research on the aspect is an important development direction of the industry in order to further widen the variety of the wafer dicing protective materials with heat resistance in the market.
Disclosure of Invention
In order to solve the problems that most of the wafer cutting protection liquids on the market at present in the background technology can improve the cutting efficiency and stability of wafers to a certain extent and avoid the problems of cutting chips or cracks and thermal stress, but a lot of heat resistance in the protection liquids is not ideal, the protection material for silicon wafer cutting provided by the invention has good film forming property and good heat resistance.
The specific scheme is as follows:
the protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 30-40 parts of water-soluble resin, 0.5-1 part of carbon nano tube, 7-12 parts of aromatic carboxylic anhydride, 3-8 parts of long-chain polyunsaturated fatty acid, 0.2-1 part of wetting agent, 0.1-1 part of defoamer, 10-20 parts of organic solvent and 40-60 parts of water.
The water-soluble resin is one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid and polyethyleneimine.
In carrying out the above embodiment, it is preferable that the molecular weight of the water-soluble resin is more than 20000.
In carrying out the above embodiments, it is preferable that the carbon nanotubes have an average diameter of 5 to 30nm and a specific surface area of 200 to 350 m/g.
In carrying out the above embodiment, preferably, the aromatic carboxylic anhydride is one or more of trimellitic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic dianhydride.
In practicing the above embodiments, the long chain polyunsaturated fatty acid is preferably one or more of omega-3 fatty acid, linoleic acid, eicosapentaenoic acid, docosahexaenoic acid.
In carrying out the above embodiment, preferably, the wetting agent is one or more of sulfonate, phosphate, monolauryl sulfate and dodecyl polyoxyethylene ether.
In carrying out the above embodiments, preferably, the antifoaming agent is one or more of polysilicon, siloxane, and polysiloxane.
In carrying out the above embodiment, preferably, the organic solvent is one or more of ethanol, n-propanol, isopropanol, propylene glycol methyl ether, ethylene glycol propyl ether, propyl formate, n-butyl acetate, and ethyl propionate.
The invention also provides a preparation method of the protective material for silicon wafer cutting, which comprises the following steps: adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoamer, organic solvent and water into a mixing container with a stirrer according to the proportion, stirring at the speed of 300-700rpm for 1.5-2.5h at normal temperature, and obtaining the protective material for silicon wafer cutting.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the protective material for silicon wafer cutting, the carbon nano tubes are added in raw material components, and a large number of physical crosslinking points can be formed between the carbon nano tubes and the water-soluble resin matrix, so that the heat resistance of the resin is improved, and meanwhile, the toughness of the resin is further enhanced; in addition, the carbon nano tube has stronger adsorption performance, thereby improving the adsorption of the protective material, and small molecular substances generated in the wafer cutting process can be adsorbed by the protective film formed by the protective material.
2. According to the protective material for silicon wafer cutting, the aromatic carboxylic anhydride is added into the raw material components, so that the heat resistance of the protective material is further improved, however, research and development personnel find that the film forming property is reduced due to the introduction of the aromatic carboxylic anhydride, and the adverse effect of the aromatic carboxylic anhydride on the film forming property of the protective material can be eliminated due to the addition of the long-chain polyunsaturated fatty acid, and through the synergistic effect of the aromatic carboxylic anhydride and the long-chain polyunsaturated fatty acid, the heat resistance of the protective material can be improved, and meanwhile, the film forming property of the protective material can also be improved.
3. The protective material for silicon wafer cutting can rapidly form a film on the surface of a wafer, has high strength after film formation, has good heat resistance, can effectively prevent condensed silicon vapor or other scraps generated in the processing process from being deposited on the surface of a chip during wafer processing, improves the quality and reliability of products, and has good film removing property.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The reagents of the examples and comparative examples are described below:
water-soluble resin: polyvinyl alcohol, guangzhou co-brightness chemical;
carbon nanotubes: korean LG;
aromatic carboxylic anhydride: trimellitic anhydride, northeast Cao Huaxue;
long chain polyunsaturated fatty acids: omega-3 fatty acids, shandong is looking for chemical industry;
wetting agent: monolauryl sulfate, a marchantia grosvenorii organism;
defoaming agent, polysiloxane and Shandong energy-accumulating chemical industry;
organic solvent, n-propanol, jinan Xueshun chemical industry.
It should be noted that, in the examples, specific techniques or conditions are not noted, and the reagents or apparatuses used, which are carried out according to techniques or conditions described in the literature in the field or according to the specifications of the products, are conventional products commercially available, and are not noted to manufacturers.
Example 1
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 30 parts of water-soluble resin, 1 part of carbon nano tube, 12 parts of aromatic carboxylic anhydride, 8 parts of long-chain polyunsaturated fatty acid, 1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 60 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at the speed of 300rpm for 2.5 hours at room temperature, filtering after stirring uniformly, and obtaining the protective material for cutting silicon wafers.
Example 2
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 0.5 part of carbon nano tube, 7 parts of aromatic carboxylic anhydride, 8 parts of long-chain polyunsaturated fatty acid, 1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 60 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 1.5h at room temperature, filtering after stirring uniformly, and obtaining the protective material for silicon wafer cutting.
Example 3
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 12 parts of aromatic carboxylic anhydride, 3 parts of long-chain polyunsaturated fatty acid, 0.2 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 60 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at 400rpm for 1.5h at room temperature, filtering after stirring uniformly to obtain the protective material for silicon wafer cutting.
Example 4
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 12 parts of aromatic carboxylic anhydride, 8 parts of long-chain polyunsaturated fatty acid, 1 part of wetting agent, 0.1 part of defoamer, 10 parts of organic solvent and 60 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at 600rpm for 2h at room temperature, stirring uniformly, and filtering to obtain the protective material for silicon wafer cutting.
Example 5
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 12 parts of aromatic carboxylic anhydride, 8 parts of long-chain polyunsaturated fatty acid, 0.2-1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 40 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 2 hours at normal temperature, uniformly stirring, and filtering to obtain the protective material for silicon wafer cutting.
Comparative example 1
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 12 parts of aromatic carboxylic anhydride, 8 parts of long-chain polyunsaturated fatty acid, 0.2-1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 40 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, aromatic carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoamer, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 2 hours at normal temperature, uniformly stirring, and filtering to obtain the protective material for silicon wafer cutting.
Comparative example 2
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 8 parts of long-chain polyunsaturated fatty acid, 0.2-1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 40 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, long-chain polyunsaturated fatty acid, wetting agent, defoamer, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 2 hours at normal temperature, uniformly stirring, and filtering to obtain the protective material for silicon wafer cutting.
Comparative example 3
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 12 parts of aromatic carboxylic anhydride, 0.2-1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 40 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, aromatic carboxylic anhydride, wetting agent, defoamer, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 2 hours at normal temperature, uniformly stirring, and filtering to obtain the protective material for silicon wafer cutting.
Comparative example 4
The protective material for silicon wafer cutting comprises the following raw materials in parts by mass: 40 parts of water-soluble resin, 1 part of carbon nano tube, 0.2-1 part of wetting agent, 1 part of defoamer, 20 parts of organic solvent and 40 parts of water.
According to the proportion, the preparation method comprises the following steps:
adding water-soluble resin, carbon nano tube, wetting agent, defoaming agent, organic solvent and water into a reaction kettle, stirring at the speed of 700rpm for 2 hours at normal temperature, uniformly stirring, and filtering to obtain the protective material for silicon wafer cutting.
The performances of the wafer cutting protection liquids obtained in examples 1 to 5 and comparative examples 1 to 4 were tested experimentally to verify the beneficial effects of the invention, and the specific tests are as follows:
1. film forming property test after the wafer cutting protective liquid of the above examples and comparative examples was obtained, the protective liquid was spin-uniformly coated on a glass slide, heated to about 110 ℃ for about 3 to 5 minutes, and observed whether the protective film was dried or not, and whether cracking was present or not.
2. After the wafer cutting protection liquid of the embodiment and the comparative example is obtained, the protection liquid is uniformly coated on a glass slide in a rotating way, and is heated to about 110 ℃ for about 3-5 minutes, so that a water-soluble protection film is formed on the surface of a silicon wafer by the protection liquid; each of the examples and comparative examples was baked in an oven at 300℃and 400℃for 30 minutes, respectively, and the state of the protective film was observed.
The test results are shown in Table 1:
TABLE 1
As can be seen from the test results of the points shown in Table 1, comparative example 1 was inferior in heat resistance test results to examples 1, which were shown to be dark yellow at 300℃and dark brown at 400℃as compared with examples 1 to 5, in which the raw material components were absent carbon nanotubes, indicating that the protective liquid was not resistant to high temperature. The invention is proved to be capable of forming a large number of physical crosslinking points with the water-soluble resin matrix by utilizing the carbon nano tube, thereby improving the heat resistance of the resin.
On the one hand, comparative example 3, which lacks long-chain polyunsaturated fatty acids in the raw material components, was found to have a poor film-forming effect and to exhibit cracking, compared with examples 1 to 5; for this purpose, comparative example 2 was designed, which contains long-chain polyunsaturated fatty acids and lacks aromatic carboxylic acid anhydrides, and which has good film formation compared with comparative example 3; in addition, comparative example 4, which does not contain a long-chain polyunsaturated fatty acid or an aromatic carboxylic anhydride, has a good film-forming effect as compared with comparative example 3. It was found from a series of comparisons that the incorporation of aromatic carboxylic anhydrides resulted in a decrease in film forming properties, whereas the addition of long chain polyunsaturated fatty acids eliminated the adverse effect of the aromatic carboxylic anhydrides on the film forming properties of the protective materials.
On the other hand, it was found that the heat resistance of comparative example 3 was due to comparative examples 2 and 4. This proves that the addition of the aromatic carboxylic anhydride further improves the heat resistance of the protective material.
From this, it is found that the synergistic effect of the long-chain polyunsaturated fatty acid and the aromatic carboxylic anhydride can improve the heat resistance of the protective material and the film forming property.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (4)

1.一种用于硅晶圆切割的保护材料,其特征在于,以质量份数计,由以下原料组成:水溶性树脂30-40份、碳纳米管0.5-1份、芳香族羧酸酐7-12份、长链多不饱和脂肪酸3-8份、润湿剂0.2-1份、消泡剂0.1-1份、有机溶剂10-20份、水40-60份;1. A protective material for silicon wafer cutting, characterized in that it consists of the following raw materials in terms of parts by mass: 30-40 parts of water-soluble resin, 0.5-1 part of carbon nanotubes, and 7 parts of aromatic carboxylic acid anhydride -12 parts, 3-8 parts of long-chain polyunsaturated fatty acids, 0.2-1 part of wetting agent, 0.1-1 part of defoaming agent, 10-20 parts of organic solvent, 40-60 parts of water; 所述碳纳米管具有5-30nm的平均直径和200m2/g-350m2/g的比表面积;The carbon nanotubes have an average diameter of 5-30nm and a specific surface area of 200m2 /g- 350m2 /g; 所述水溶性树脂的分子量大于20000,所述水溶性树脂为聚乙烯醇;The molecular weight of the water-soluble resin is greater than 20,000, and the water-soluble resin is polyvinyl alcohol; 所述长链多不饱和脂肪酸为ω-3脂肪酸;The long-chain polyunsaturated fatty acids are omega-3 fatty acids; 所述芳香族羧酸酐为偏苯三甲酸酐、均苯四甲酸酐和联苯四甲酸二酐中的一种或多种;The aromatic carboxylic acid anhydride is one or more of trimellitic anhydride, pyromellitic anhydride and diphenyltetracarboxylic dianhydride; 所述有机溶剂为乙醇、正丙醇、异丙醇、丙二醇甲醚、乙二醇丙醚、甲酸丙酯、乙酸正丁酯和丙酸乙酯中的一种或多种。The organic solvent is one or more of ethanol, n-propyl alcohol, isopropyl alcohol, propylene glycol methyl ether, ethylene glycol propyl ether, propyl formate, n-butyl acetate and ethyl propionate. 2.根据权利要求1所述的用于硅晶圆切割的保护材料,其特征在于,所述润湿剂为磺酸盐、磷酸酯、单月桂醇硫酸酯和十二烷基聚氧乙烯醚中的一种或多种。2. The protective material for silicon wafer cutting according to claim 1, characterized in that the wetting agent is sulfonate, phosphate ester, monolauryl sulfate and lauryl polyoxyethylene ether. one or more of them. 3.根据权利要求1所述的用于硅晶圆切割的保护材料,其特征在于,所述消泡剂为多晶硅和硅氧烷中的一种或多种。3. The protective material for silicon wafer cutting according to claim 1, characterized in that the defoaming agent is one or more of polysilicon and siloxane. 4.一种如权利要求1-3任意一项所述的用于硅晶圆切割的保护材料的制备方法,其特征在于,其步骤包括:按配比将水溶性树脂、碳纳米管、芳香族羧酸酐、长链多不饱和脂肪酸、润湿剂、消泡剂、有机溶剂、水加入到设有搅拌机的混合容器内,在常温下以300-700rpm的速度搅拌1.5-2.5 h,制得用于硅晶圆切割的保护材料。4. A method for preparing protective materials for silicon wafer cutting according to any one of claims 1-3, characterized in that the steps include: mixing water-soluble resin, carbon nanotubes, aromatic Carboxylic anhydride, long-chain polyunsaturated fatty acid, wetting agent, defoaming agent, organic solvent, and water are added into a mixing container equipped with a stirrer, and stirred at a speed of 300-700 rpm for 1.5-2.5 hours at room temperature to prepare Protective material for silicon wafer cutting.
CN202211474781.9A 2022-11-23 2022-11-23 Protective material for silicon wafer cutting and preparation method thereof Active CN115895356B (en)

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Patentee after: Kunshan Hanpin Electronics Co.,Ltd.

Country or region after: China

Address before: No. 2008 Shuixiu Road, Yushan Town, Kunshan City, Suzhou City, Jiangsu Province

Patentee before: HANPING (KUNSHAN) ELECTRONIC Co.,Ltd.

Country or region before: China

CP03 Change of name, title or address