Bonding glue, preparation method and application

Abstract

The invention discloses bonding glue, a preparation method and application, and belongs to the technical field of bonding glue. According to the bonding adhesive provided by the embodiment of the invention, the styrene-ethylene-butylene-styrene block copolymer and the rosin modified resin are compounded, and the styrene-ethylene-butylene-styrene block copolymer and the rosin modified resin both have relatively good high-temperature resistance and play a synergistic effect; therefore, the temperature resistance of the bonding glue is effectively improved.

Description

Technical Field

[0001] This application relates to the technical field of bonding adhesives, and particularly to a bonding adhesive, a preparation method and an application thereof. Background Art

[0002] At present, semiconductor chips are gradually developing towards faster processing speeds and smaller volumes. In order to reduce the volume of semiconductor chips, wafer thinning technology has become crucial. The purpose of wafer thinning is to reduce the thickness of the chip, and this process may affect the mechanical stability of the wafer, thereby increasing the risk of warping, bending or even cracking. In order to reduce the risk of warping, bending or even cracking of the wafer, temporary bonding technology is widely used. This technology bonds the wafer to be processed and the carrier wafer using a temporary bonding adhesive to provide support for the wafer during the processing, reducing the warping phenomenon. After the processing is completed, the wafer and the carrier wafer are separated through a thermal slip debonding technology.

[0003] Due to the high debonding temperature, the performance of the temporary bonding adhesives in the related technologies deteriorates at high temperatures, which limits their application in high-temperature processes. Summary of the Invention

[0004] Embodiments of this application provide a bonding adhesive, a preparation method and an application thereof, and the bonding adhesive has excellent high-temperature resistance. The technical solution is as follows:

[0005] On the one hand, a bonding adhesive is provided, and the bonding adhesive comprises the following components in parts by mass:

[0006] 10 - 30 parts of styrene-ethylene-butene-styrene block copolymer, 20 - 40 parts of rosin modified resin, 0.1 - 10 parts of leveling agent, 40 - 70 parts of solvent;

[0007] Among them, the styrene-ethylene-butene-styrene block copolymer is a linear triblock copolymer with polystyrene as the end segment and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic segment.

[0008] In a possible implementation manner, the mass ratio of the styrene-ethylene-butene-styrene block copolymer to the rosin modified resin is 0.25 - 1.5.

[0009] In another possible implementation manner, the styrene / rubber ratio in the styrene-ethylene-butene-styrene block copolymer is 30% - 67%, and the diblock content is 0.5% - 32%.

[0010] In another possible implementation manner, the weight average molecular weight range of the styrene-ethylene-butene-styrene block copolymer is 150000 - 400000 g / mol.

[0011] In another possible implementation, the rosin-modified resin includes at least one of rosin-modified phenolic resin, rosin-modified maleic resin, hydrogenated rosin, and rosin-modified polyurethane.

[0012] In another possible implementation, the weight-average molecular weight range of the rosin-modified resin is 750 - 2500 g / mol.

[0013] In another possible implementation, the leveling agent includes at least one of Tech-2046, MF-A X 50S, Glide-450, and WE-D8900N.

[0014] In another possible implementation, the solvent includes at least one of toluene, butyl acetate, cyclohexane, isobutyl acetate, n-butyl acetate, xylene, n-octane, decahydronaphthalene, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

[0015] On the other hand, a preparation method of the bonding adhesive is provided, and the preparation method includes:

[0016] Mix the solvent and the leveling agent evenly according to the mass parts of each component to obtain a mixed solution;

[0017] Add the rosin-modified resin to the mixed solution and mix evenly to obtain a precursor;

[0018] Heat the precursor to 40 - 50 °C, add the styrene-ethylene-butene-styrene block copolymer, and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0019] On the other hand, an application of the bonding adhesive in wafer processing is provided.

[0020] The embodiment of the present application provides a bonding adhesive, which is a compound of a styrene-ethylene-butene-styrene block copolymer and a rosin-modified resin. Both the styrene-ethylene-butene-styrene block copolymer and the rosin-modified resin have good high-temperature resistance, and they play a synergistic role, thereby effectively improving the temperature resistance of the bonding adhesive.

[0021] It should be understood that the above general description and the following detailed description are only exemplary and do not limit the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a device structure diagram provided by the embodiment of the present application;

[0023] Figure 2 is a schematic diagram of applying the bonding adhesive during wafer processing provided by the embodiment of the present application. Detailed implementation manners

[0024] To make the technical solutions and advantages of this application clearer, the following further describes the implementation manners of this application in detail.

[0025] On the one hand, the embodiment of this application provides a bonding adhesive, which includes the following components in parts by mass:

[0026] 10-30 parts of styrene-ethylene-butene-styrene block copolymer (SEBS), 20-40 parts of rosin modified resin, 0.1-10 parts of leveling agent, and 40-70 parts of solvent;

[0027] Among them, the styrene-ethylene-butene-styrene block copolymer (SEBS) is a linear triblock copolymer with polystyrene as the terminal segment and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic segment.

[0028] SEBS has attracted much attention due to its good rubber elasticity, excellent weather resistance and heat resistance. The rosin modified resin has excellent aging resistance, corrosion resistance and adhesiveness, and has better softening performance than general resins, and can effectively realize the function of low-temperature thermal slip debonding.

[0029] The bonding adhesive provided by the embodiment of this application combines the styrene-ethylene-butene-styrene block copolymer and the rosin modified resin. Both the styrene-ethylene-butene-styrene block copolymer and the rosin modified resin have good high-temperature resistance, and they play a synergistic role, thereby effectively improving the heat resistance of the bonding adhesive.

[0030] It should be noted that the bonding adhesive in the related technology has insufficient chemical resistance and cannot remain stable in a variety of chemical processes. For example, WaferBond HT-10.10 of Brewer Science is not resistant to concentrated sulfuric acid and concentrated hydrochloric acid. And the SEBS in the bonding adhesive provided by this application has good chemical resistance. Because the content of unsaturated bonds in its structure is low, it can effectively resist the erosion of various chemical substances. And the rosin modified resin also has high corrosion resistance and can remain stable in a chemical solution environment. Therefore, the bonding adhesive provided by this application has good chemical resistance.

[0031] Moreover, the bonding adhesive in the related technology has poor dimensional stability at high temperatures, which may affect the accuracy and quality of wafer processing. And the SEBS in the bonding adhesive provided by this application has excellent compression set resistance. By compounding with the rosin modified resin, the dimensional stability of the bonding adhesive at high temperatures can be further improved, so that it maintains a good shape at high temperatures.

[0032] In addition, the bonding adhesives in the related art have processing defects, and defects such as bubbles or delamination may occur in processes such as CMP (Chemical Mechanical Polishing), affecting the product performance. However, SEBS in the bonding adhesive provided in this application itself has good processing performance. By compounding with a rosin-modified resin in an appropriate proportion, the risk of generating bubbles and delamination in processes such as CMP (Chemical Mechanical Polishing) can be reduced. Moreover, the addition of the rosin-modified resin can also improve the uniformity of the coating film and reduce defects.

[0033] Furthermore, the bonding adhesives in the related art have a relatively high viscosity at high temperatures, resulting in an increase in the bonding and debonding temperatures, which is not conducive to energy conservation and production efficiency improvement. And some bonding adhesives are prone to generating "snowflake-like" defects or delamination of bonding pairs in high-temperature processes, affecting the wafer processing quality. However, the bonding adhesive provided in this application compounds SEBS with a rosin-modified resin, which can reduce the defects generated in high-temperature processes. The heat resistance of SEBS combined with the thermal stability of the rosin-modified resin can effectively prevent thermal decomposition and chemical structure changes at high temperatures, thereby reducing the problems of "snowflake-like" defects or delamination of bonding pairs.

[0034] In a possible implementation manner, the mass parts of SEBS can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts. Specifically, the mass parts of SEBS can be 15 to 20 parts.

[0035] In a possible implementation manner, the styrene / rubber ratio in SEBS is 30% - 67%, and the diblock content is 0.5% - 32%.

[0036] In this implementation manner, the styrene / rubber ratio can be 30%, 35%, 37%, 38%, 40%, 43%, 45%, 47%, 50%, 53%, 55%, 60%, 62%, 65%, 67%. Specifically, the styrene / rubber ratio can be 40% - 50%.

[0037] The diblock content can be 0.5%, 1%, 5%, 10%, 13%, 14%, 15%, 20%, 22%, 25%, 28%, 30%, 31%, 32%. Specifically, the diblock content can be 13% - 32%.

[0038] In the embodiments of this application, the influence of the styrene / rubber ratio and the diblock content on SEBS is mainly reflected in the following aspects:

[0039] ① Mechanical properties: The higher the styrene / rubber ratio, the more physical entanglement points can be provided for SEBS, enhancing the mechanical properties of the material and the higher its tensile strength.

[0040] ②Processing performance: An appropriate amount of diblock SB (styrene-butadiene) is beneficial to processing because when the diblock SB and SBS (styrene-butadiene-styrene block copolymer) undergo phase separation, the two segments of SB enter the corresponding micro-regions of SBS. When the mass fraction is small, it does not destroy the network structure, but increases high-temperature fluidity.

[0041] SBS is a triblock copolymer of styrene and butadiene containing unsaturated double bonds. SEBS (styrene-ethylene / butylene-styrene block copolymer) is a hydrogenated product of SBS. By hydrogenating the unsaturated double bonds of the butadiene segment in SBS, a random copolymer of ethylene and butene is formed.

[0042] It should be noted that a star-shaped polymer refers to multiple polymer chains (usually three or more) radiating from a common center point, forming a star-like morphology. This structure is characterized by a central core from which multiple polymer chains extend outward. Due to their structural characteristics, star-shaped polymers generally have good processing performance and unique physical properties. The SEBS used in this application has a star-shaped structure, and therefore, it has good processing performance and unique physical properties.

[0043] In a possible implementation, the weight average molecular weight of SEBS ranges from 150,000 to 400,000 g / mol.

[0044] In this implementation, the weight average molecular weight of SEBS can be 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, or 400,000 g / mol.

[0045] In the embodiments of the present application, the weight-average molecular weight of SEBS affects the mechanical properties, permanent compression set performance, flow properties, etc. of SEBS. When the weight-average molecular weight is high, the tensile strength and elongation at break of the product will also be higher. When the weight-average molecular weight is low, the permanent compression set performance will increase with the SEBS molecular weight, and the permanent compression set will decrease. After its molecular weight increases to a certain extent, the influence of the permanent compression set molecular weight and molecular structure is small. The higher the molecular weight, the worse the flow properties. At the same molecular weight, SEBS with a star structure has better flowability.

[0046] In one possible implementation, the mass fraction of the rosin-modified resin may be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, or 40 parts. Specifically, the mass fraction of the rosin-modified resin may be 20 to 30 parts.

[0047] In a possible implementation, the rosin modified resin includes at least one of rosin modified phenolic resin, rosin modified maleic resin, hydrogenated rosin, and rosin modified polyurethane. Specifically, the rosin modified resin may be rosin modified maleic resin.

[0048] Among them, the rosin modified phenolic resin is obtained by directly reacting raw materials such as phenol and aldehyde with rosin, carrying out a polycondensation reaction under the action of an alkaline catalyst, gradually raising the temperature to remove water, during which a Diels - Alder addition reaction occurs between the condensate and rosin acid, and adding a polyol to carry out an esterification reaction under the action of a catalyst, thereby obtaining the rosin modified phenolic resin.

[0049] The rosin modified maleic resin is a modified resin obtained by esterifying the adduct of rosin and maleic anhydride with a polyol, and the resulting modified resin is called rosin maleic anhydride polyol ester, in which there are more maleic rosin products.

[0050] Hydrogenated rosin is formed by saturating part or all of the conjugated double bonds of abietic acid - type resin acids in rosin with hydrogen under the action of a catalyst at a certain temperature and pressure. The rosin partially saturated with hydrogen is called dihydro rosin, generally known as hydrogenated rosin.

[0051] The rosin modified polyurethane is to modify the water - borne polyurethane using the tricyclic phenanthrene skeleton structure of rosin, and add rosin to the polyurethane through reactions such as esterification to obtain a rosin modified polyurethane with good heat resistance and mechanical strength.

[0052] In a possible implementation, the weight - average molecular weight range of the rosin modified resin is 750 - 2500 g / mol.

[0053] In this implementation, the weight - average molecular weight of the rosin modified resin can be 750 g / mol, 800 g / mol, 900 g / mol, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2500 g / mol.

[0054] In the embodiments of the present application, the rosin modified resin within the above weight - average molecular weight range has high corrosion resistance, heat resistance, and thermal stability. When compounded with SEBS, it helps to improve the chemical resistance, heat resistance, dimensional stability at high temperature of the bonding adhesive, and reduce the defects generated during the high - temperature process.

[0055] In the embodiments of the present application, the mass ratio of SEBS to the rosin modified resin is 0.25 - 1.5.

[0056] Among them, the mass ratio of SEBS to the rosin-modified resin can be 0.25, 0.3, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5. Specifically, the mass ratio of SEBS to the rosin-modified resin is 0.4 to 1.

[0057] In the embodiments of the present application, the compounding of SEBS and the rosin-modified resin within the above mass ratio range can maximize the chemical resistance, heat resistance, dimensional stability at high temperature of the bonding adhesive, and reduce the defects generated during the high-temperature process.

[0058] In a possible implementation, the mass parts of the leveling agent can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts. Specifically, the mass parts of the leveling agent can be 0.5 to 1 part.

[0059] In a possible implementation, the leveling agent includes at least one of Tech-2046, MF-AX 50S, Glide-450, and WE-D8900N. Specifically, the leveling agent can be Tech-2046.

[0060] In the embodiments of the present application, adding the above leveling agent can significantly improve the construction performance and film-forming effect of the bonding adhesive, and eliminate the defects on the surface of the coating film.

[0061] In a possible implementation, the mass parts of the solvent can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts. Specifically, the mass parts of the solvent can be 50 to 70 parts.

[0062] In a possible implementation, the solvent includes at least one of toluene, butyl acetate, cyclohexane, isobutyl acetate, n-butyl acetate, xylene, n-octane, decalin, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. Specifically, the solvent is isobutyl acetate and cyclohexane.

[0063] In the embodiments of the present application, using the above solvent not only facilitates the dissolution of SEBS and the rosin-modified resin, but also has low toxicity and does not affect the properties such as the aging resistance and heat resistance of the resin.

[0064] In summary, the bonding adhesive provided by the present application has the function of low-temperature pyrolysis, and can easily separate the device wafer from the carrier wafer through the thermal slip method at 120 °C. The bonding adhesive also has good corrosion resistance and bonding strength, and the bonding adhesive remaining on the surface of the device wafer after debonding can be easily completely removed. The bonding adhesive also has excellent thermal stability and chemical stability, is convenient for post-treatment, and is easy to process. The appearance of the bonding adhesive provided by the present application not only solves the problem of thermal budget limitation in the prior art, but also provides chemical solvent tolerance, and improves the uniformity and film thickness control ability of the bonding adhesive, providing a new solution for the key materials in the semiconductor manufacturing process.

[0065] On the other hand, the embodiment of the present application provides a preparation method of a bonding adhesive, and the preparation method includes:

[0066] Step 1: According to the mass parts of each component, mix the solvent and the leveling agent evenly to obtain a mixed solution.

[0067] According to the mass parts of each component, add the solvent and the leveling agent to the stirring kettle, stir and mix evenly to obtain a mixed solution.

[0068] In this step, the stirring rate can be 80-100 r / min. For example, the stirring rates are 80 r / min, 82 r / min, 85 r / min, 88 r / min, 90 r / min, 92 r / min, 95 r / min, 98 r / min, 100 r / min.

[0069] The stirring time can be 20-30 min. For example, the stirring times are 20 min, 21 min, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min, 30 min.

[0070] Step 2: Add the rosin-modified resin to the mixed solution and mix evenly to obtain a precursor.

[0071] At room temperature, add the rosin-modified resin to the mixed solution and stir until a clear and transparent liquid is formed to obtain a precursor.

[0072] In this step, the stirring rate can be 500-600 r / min. For example, the stirring rates are 500 r / min, 510 r / min, 520 r / min, 530 r / min, 540 r / min, 550 r / min, 560 r / min, 570 r / min, 580 r / min, 590 r / min, 600 r / min.

[0073] The stirring time can be 480 - 600 min. For example, the stirring time can be 480 min, 490 min, 500 min, 510 min, 520 min, 530 min, 540 min, 550 min, 560 min, 570 min, 580 min, 590 min, 600 min.

[0074] Step 3: Heat the precursor to 40 - 50 °C, add SEBS, and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0075] The heating temperature can be 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, 46 °C, 47 °C, 48 °C, 49 °C, 50 °C. Specifically, the heating temperature can be 40 - 45 °C.

[0076] The stirring rate and time in this step can be the same as or different from those in Step 2, and no specific limitation is made thereto.

[0077] In the embodiments of the present application, high-speed stirring and shearing are adopted to increase its surface energy and form microcolloidal particles, which are uniformly dispersed in the system.

[0078] The preparation process provided by the present application is simple and efficient. Through specific stirring and mixing techniques, it can ensure the uniform dispersion of each component of the bonding adhesive, optimize the coating uniformity and the thickness uniformity (TTV) of the film. This preparation method not only improves production efficiency but also reduces costs, making the entire production process more economically feasible.

[0079] On the other hand, the embodiments of the present application provide an application of the bonding adhesive in wafer processing.

[0080] In the embodiments of the present application, the spin coating construction method of the bonding adhesive is as follows:

[0081] (1) Place the wafer in the spin coater, turn on the vacuum system, fix the wafer with the chuck, and set the spin coating speed to 1000 - 3000 r / min.

[0082] Among them, the spin coating speed can be 1000 r / min, 1500 r / min, 1600 r / min, 1700 r / min, 1800 r / min, 1900 r / min, 2000 r / min, 2100 r / min, 2200 r / min, 2300 r / min, 2400 r / min, 2500 r / min, 3000 r / min. Specifically, the spin coating speed can be 1500 - 2000 r / min.

[0083] Among them, the wafer can be a sapphire wafer or other types of wafers, and no specific limitation is made thereto.

[0084] (2) Absorb a certain volume of bonding glue, evenly drip the glue to the center of the wafer, and spin coat for 30 to 50 seconds.

[0085] The volume of the bonding glue can be set and changed as needed, and is not specifically limited thereto. For example, the volume of the bonding glue is 4 mL, 5 mL, or 6 mL.

[0086] In one possible implementation, the coating amount of the bonding adhesive may be 4-8 g / 70-100 cm 2 .

[0087] In this implementation, the coating amount of bonding glue can be 4g / 70cm 2 、4g / 80cm 2 、4g / 90cm 2 , 4g / 100cm 2 , 5g / 70cm 2 , 5g / 80cm 2 , 5g / 90cm 2 , 5g / 100cm 2 、6g / 70cm 2 、6g / 80cm 2 、6g / 90cm 2 , 6g / 100cm 2 , 7g / 70cm 2 , 7g / 80cm 2 , 7g / 90cm 2 , 7g / 100cm 2 , 8g / 70cm 2 , 8g / 80cm 2 、8g / 90cm 2 , 8g / 100cm 2 .

[0088] The spin coating time may be 30s, 32s, 35s, 38s, 40s, 42s, 45s, 48s, or 50s. Specifically, the spin coating time may be 30 to 40s.

[0089] (3) Close the vacuum chuck, remove the wafer coated with bonding glue, and bake it in a 130°C oven for 300 to 500 seconds.

[0090] The baking time can be 300s, 350s, 400s, 450s, or 500s.

[0091] (4) After baking, place the adhesive-coated side of the wafer on the surface of the wafer carrier, heat at 100-150°C and bond under 2kg pressure for 4-10 minutes, and cool to room temperature to complete the temporary bonding of the wafer.

[0092] The heating temperature can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C.

[0093] The bonding time can be 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min. Specifically, the bonding time can be 5 - 7 min.

[0094] See Figure 1 , Figure 1 for the device structure diagram. Among them, 1 is the base layer of the tape core structure, which can be sapphire, glass, silicon wafer, etc.; 2 is the adhesive layer; 3 is the base layer, which can be sapphire, glass, silicon wafer, etc.; 4 is single - core, micro - device, etc.

[0095] See Figure 2 , Figure 2 shown is a schematic diagram of applying the bonding adhesive during the wafer processing. First, take a wafer, spin - coat the bonding adhesive provided in Example 4 below on it, and after baking, send it into a thermocompression bonder. In a vacuum environment, heat to soften the bonding adhesive, and then apply pressure on both sides to bond the wafer and the carrier plate together to form a bonded pair. For the bonded pair, perform related processes such as back - grinding, RDL (Redistribution Layer), thin - film, and ball - planting, etc. When it is necessary to disassemble the bonded pair after all processes are completed, heat the upper and lower plates of the bonded pair to soften the bonding adhesive, and then apply a shear force to the upper and lower plates to make the bonded pair slide and disassemble, and finally clean the residual adhesive on the wafer. Among them, the specific composition of Example 4 will be introduced later and will not be elaborated here for the time being.

[0096] In the embodiments of the present application, the storage conditions of the bonding adhesive are as follows: The container is sealed and stored in a low - temperature, dry, and well - ventilated place. When the product is not in use, keep the container closed and upright. Keep away from fire, light, heat sources, and it is prohibited to store it mixed with strong acids, strong alkalis, and strong oxidants. The storage time is starting from the date when the sample is prepared, and the use time is within one natural year.

[0097] By specifying the storage conditions and period of the bonding adhesive, the present application can ensure the long - term stability and effective use period of the bonding adhesive, and further reduce the cost expenditure in long - term operation.

[0098] To make the technical solutions and advantages of the present application clearer, the following will be elaborated in detail through specific embodiments.

[0099] In the following specific embodiments, for the operations not specified in conditions, they are all carried out according to conventional conditions or the conditions recommended by the manufacturer. The raw materials not specified in the manufacturer and specifications are all conventional products that can be obtained through commercial purchase.

[0100] Example 1

[0101] Example 1 provides a bonding adhesive, which is prepared by the following method:

[0102] Mix 15 parts by mass of toluene, 55 parts by mass of xylene, and 1 part by mass of MF-A X 50S evenly; at room temperature, add 20 parts by mass of hydrogenated rosin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 40 °C, and add 30 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0103] Among them, the styrene / rubber ratio in SEBS is 67%, the diblock content is 24%, and the weight average molecular weight of SEBS is 3.5×10 5 , and the weight average molecular weight of hydrogenated rosin is 2.3×10 3 .

[0104] Example 2

[0105] Example 2 provides a bonding adhesive, which is prepared by the following method:

[0106] Mix 26 parts by mass of n-butyl acetate, 43 parts by mass of toluene, and 2 parts by mass of Glide-450 evenly; at room temperature, add 24 parts by mass of rosin-modified maleic resin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 26 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0107] Among them, the styrene / rubber ratio in SEBS is 44%, the diblock content is 1%, and the weight average molecular weight of SEBS is 2.5×10 5 , and the weight average molecular weight of rosin-modified maleic resin is 1.3×10 3 .

[0108] Example 3

[0109] Example 3 provides a bonding adhesive, which is prepared by the following method:

[0110] Mix 23 parts by mass of n-butyl acetate, 45 parts by mass of toluene, and 5 parts by mass of WE-D8900N evenly; at room temperature, add 28 parts by mass of rosin-modified polyurethane under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 20 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0111] Among them, the styrene / rubber ratio in SEBS is 47%, the diblock content is 7%, and the weight average molecular weight of SEBS is 2.5×10 5, the weight-average molecular weight of the rosin-modified polyurethane is 2.5×10 3 .

[0112] Example 4

[0113] Example 4 provides an adhesive, which is prepared by the following method:

[0114] Mix 19 parts by mass of isobutyl acetate, 43 parts by mass of n-octane and 1 part by mass of Tech-2046 evenly; at room temperature, add 30 parts by mass of rosin-modified maleic resin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 17 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain the adhesive.

[0115] Among them, the styrene / rubber ratio in SEBS is 42%, the diblock content is 0.5%, and the weight-average molecular weight of SEBS is 2.3×10 5 , the weight-average molecular weight of the rosin-modified maleic resin is 1.8×10 3 .

[0116] Example 5

[0117] Example 5 provides an adhesive, which is prepared by the following method:

[0118] Mix 34 parts by mass of ethylene glycol monobutyl ether, 32 parts by mass of dipropylene glycol monomethyl ether and 0.5 part by mass of Glide-450 evenly; at room temperature, add 29 parts by mass of hydrogenated rosin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 16 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain the adhesive.

[0119] Among them, the styrene / rubber ratio in SEBS is 43%, the diblock content is 0.5%, and the weight-average molecular weight of SEBS is 2.3×10 5 , the weight-average molecular weight of the hydrogenated rosin is 1.0×10 3 .

[0120] Example 6

[0121] Example 6 provides an adhesive, which is prepared by the following method:

[0122] Mix 45 parts by mass of decalin, 18 parts by mass of ethylene glycol monobutyl ether, and 0.7 part by mass of Glide-450 evenly; at room temperature, add 25 parts by mass of rosin-modified polyurethane under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 42 °C, and add 15 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0123] Among them, the styrene / rubber ratio in SEBS is 30%, the diblock content is 7%, and the weight-average molecular weight of SEBS is 2.1×10 5 , and the weight-average molecular weight of hydrogenated rosin is 2.1×10 3 .

[0124] Example 7

[0125] Example 7 provides a bonding adhesive, which is prepared by the following method:

[0126] Mix 24 parts by mass of isobutyl acetate, 40 parts by mass of cyclohexane, and 1 part by mass of MF-AX 50S evenly; at room temperature, add 32 parts by mass of hydrogenated rosin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 43 °C, and add 12 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0127] Among them, the styrene / rubber ratio in SEBS is 47%, the diblock content is 0.5%, and the weight-average molecular weight of SEBS is 2.4×10 5 , and the weight-average molecular weight of hydrogenated rosin is 1.2×10 3 .

[0128] Example 8

[0129] Example 8 provides a bonding adhesive, which is prepared by the following method:

[0130] Mix 25 parts by mass of isobutyl acetate, 43 parts by mass of xylene, and 0.6 part by mass of Tech-2046 evenly; at room temperature, add 32 parts by mass of rosin-modified maleic resin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 10 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0131] Among them, the styrene / rubber ratio in SEBS is 67%, the diblock content is 0.5%, and the weight-average molecular weight of SEBS is 3×10 5 , and the weight-average molecular weight of hydrogenated rosin is 1.5×10 3 .

[0132] Example 9

[0133] Example 9 provides a bonding adhesive, which is prepared by the following method:

[0134] Mix 22 parts by mass of n-octane, 46 parts by mass of cyclohexane and 1 part by mass of Tech-2046 evenly; at room temperature, add 26 parts by mass of hydrogenated rosin under continuous stirring and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C and add 20 parts by mass of SEBS under continuous stirring and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0135] Among them, the styrene / rubber ratio in SEBS is 67%, the diblock content is 7%, and the weight-average molecular weight of SEBS is 3.1×10 5 , and the weight-average molecular weight of hydrogenated rosin is 1.2×10 3 .

[0136] Example 10

[0137] Example 10 provides a bonding adhesive, which is prepared by the following method:

[0138] Mix 21 parts by mass of xylene, 45 parts by mass of cyclohexane and 5 parts by mass of MF-AX 50S evenly; at room temperature, add 24 parts by mass of rosin-modified polyurethane under continuous stirring and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C and add 17 parts by mass of SEBS under continuous stirring and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0139] Among them, the styrene / rubber ratio in SEBS is 36%, the diblock content is 13%, and the weight-average molecular weight of SEBS is 2.4×10 5 , and the weight-average molecular weight of hydrogenated rosin is 2.1×10 3 .

[0140] Example 11

[0141] Example 11 provides a bonding adhesive, which is prepared by the following method:

[0142] Mix 20 parts by mass of n-butyl acetate, 35 parts by mass of cyclohexane and 10 parts by mass of Tech-2046 evenly; at room temperature, add 26 parts by mass of rosin-modified maleic resin under continuous stirring and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C and add 20 parts by mass of SEBS under continuous stirring and stir until a clear and transparent liquid is formed to obtain the bonding adhesive.

[0143] Among them, the styrene / rubber ratio in SEBS is 41%, the diblock content is 14%, and the weight-average molecular weight of SEBS is 2.3×105 The weight average molecular weight of hydrogenated rosin is 1.6×10 3 .

[0144] Example 12

[0145] Example 12 provides a bonding adhesive, which is prepared by the following method:

[0146] 24 parts by mass of dipropylene glycol methyl ether, 43 parts by mass of toluene and 3 parts by mass of Glide-450 were mixed uniformly; 37 parts by mass of rosin-modified polyurethane were added under continuous stirring at room temperature, and stirred until a clear and transparent liquid was formed to obtain a precursor; the precursor was heated to 45°C, 15 parts by mass of SEBS were added under continuous stirring, and stirred until a clear and transparent liquid was formed to obtain a bonding adhesive.

[0147] The styrene / rubber ratio in SEBS is 44%, the diblock content is 7%, and the weight average molecular weight of SEBS is 2.7×10 5 The weight average molecular weight of hydrogenated rosin is 1.6×10 3 .

[0148] Example 13

[0149] Example 13 provides a bonding adhesive, which is prepared by the following method:

[0150] 21 parts by mass of isobutyl acetate, 39 parts by mass of ethylene glycol butyl ether and 1 part by mass of Tech-2046 were mixed evenly; 24 parts by mass of rosin-modified maleic acid resin were added under continuous stirring at room temperature, and stirred until a clear and transparent liquid was formed to obtain a precursor; the precursor was heated to 45°C, 20 parts by mass of SEBS were added under continuous stirring, and stirred until a clear and transparent liquid was formed to obtain a bonding adhesive.

[0151] The styrene / rubber ratio in SEBS is 45%, the diblock content is 8%, and the weight average molecular weight of SEBS is 2.7×10 5 The weight average molecular weight of hydrogenated rosin is 1.8×10 3 .

[0152] Example 14

[0153] Example 14 provides a bonding adhesive, which is prepared by the following method:

[0154] Mix 21 parts by mass of butyl acetate, 42 parts by mass of ethylene glycol monobutyl ether, and 0.4 part by mass of WE-D8900N evenly; at room temperature, add 30 parts by mass of hydrogenated rosin under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 17 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0155] Among them, the styrene / rubber ratio in SEBS is 67%, the diblock content is 0.5%, and the weight-average molecular weight of SEBS is 3×10 5 , and the weight-average molecular weight of hydrogenated rosin is 2.0×10 3 .

[0156] Comparative Example 1

[0157] Comparative Example 1 provides a bonding adhesive, which is prepared by the following method:

[0158] Mix 20 parts by mass of butyl acetate, 35 parts by mass of cyclohexane, and 1 part by mass of Tech-2046 evenly; at room temperature, add 30 parts by mass of rosin-modified glycerol ester under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a precursor; heat the precursor to 45 °C, and add 23 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0159] Among them, the styrene / rubber ratio in SEBS is 67%, the diblock content is 24%, and the weight-average molecular weight of SEBS is 3.5×10 5 , and the weight-average molecular weight of hydrogenated rosin is 2.0×10 3 .

[0160] Comparative Example 2

[0161] Comparative Example 2 provides a bonding adhesive, which is prepared by the following method:

[0162] Mix 21 parts by mass of isobutyl acetate, 39 parts by mass of ethylene glycol monobutyl ether, and 1 part by mass of Tech-2046 evenly; then heat to 45 °C, and add 24 parts by mass of SEBS under continuous stirring, and stir until a clear and transparent liquid is formed to obtain a bonding adhesive.

[0163] Among them, the styrene / rubber ratio in SEBS is 70%, the diblock content is 13%, and the weight-average molecular weight of SEBS is 4.5×10 5 .

[0164] The compositions of the bonding adhesives corresponding to Examples 1 to 14 and Comparative Examples 1 to 2 can also be seen in Table 1 below.

[0165] Table 1

[0166]

[0167]

[0168]

[0169] This application tested the bonding adhesives prepared in Examples 1-14 and Comparative Examples 1-2. The test results are shown in Table 2 below.

[0170] Table 2

[0171]

[0172]

[0173] In this application, the homogeneity and TTV of Examples 1-14 and Comparative Examples 1-2 were tested by micrometer. The test methods and evaluation criteria are as follows:

[0174] 1. Prepare a high-precision micrometer test instrument to ensure that the instrument has been calibrated and meets the test requirements. In addition, prepare a sample to be tested to ensure that its surface is flat and has no obvious defects or damages. Among them, the sample is an unbonded wafer and a bonded pair after bonding.

[0175] 2. Firmly clamp the sample to be tested on the test bench to ensure that it will not move or shake during the test to ensure the accuracy of the test results.

[0176] 3. Set the test parameters according to the requirements and actual situation of the sample to ensure that the setting of the test parameters meets the test requirements and can meet the accurate evaluation of homogeneity and TTV.

[0177] 4. Start the micrometer test instrument and start testing the surface of the sample. The instrument will collect and display the height change data of the sample surface in real time, and analyze the homogeneity and TTV of the sample surface through these data.

[0178] 5. Evaluation criteria: Homogeneity < 3%, TTV < 3μm.

[0179] In this application, the high-temperature stability test method for Examples 1-14 and Comparative Examples 1-2 is thermogravimetric analysis. The test method is as follows:

[0180] 1. Prepare the sample to be tested to ensure that its solvent is volatilized as much as possible. By testing the weight loss of the sample at a fixed heating rate, the weight loss of the test sample at different temperatures can be determined, and the temperature at which the sample mass loss is 5% can be determined.

[0181] 2. Prepare the same samples to be tested and ensure that their solvents are volatilized as much as possible. Measure the time it takes for the sample to lose 5% of its weight at a fixed temperature. Based on the measured time, it can be considered that the sample is stable during this period of time at this temperature. Among them, the sample to be tested is the bonded pair after bonding.

[0182] The thermal debonding test method for the bonded pair of the present application is as follows:

[0183] 1. Place the wafer and the carrier wafer in a thermal debonding device and heat to the melting temperature of the bonding medium.

[0184] 2. Control the viscosity of the bonding medium by adjusting the temperature so that while keeping the wafer stable, slip debonding can be achieved.

[0185] 3. While heating, thermal debonding can be achieved by horizontally sliding the carrier wafer, or in some cases, by pushing and pulling actions in the vertical direction to complete thermal debonding.

[0186] It can be seen from Table 2 that when preparing the bonding adhesive by compounding SEBS and the rosin-modified resin in Examples 1 to 14 and Comparative Example 1, good debonding can be achieved, while in Comparative Example 2, only SEBS is used to prepare the bonding adhesive and debonding cannot be achieved. Thus, it can be shown that using SEBS alone cannot achieve debonding.

[0187] Moreover, after the rosin-modified resin used in Examples 1 to 14 is compounded with SEBS, the prepared bonding adhesive has good high-temperature resistance. However, in Comparative Example 1, the rosin-modified resin used is rosin-modified glycerol ester, which is not heat-resistant. Therefore, the bonding adhesive prepared after its compounding with SEBS is also not heat-resistant. Thus, it can be shown that the rosin-modified resin used in the present application has good high-temperature resistance, and the bonding adhesive prepared after its compounding with SEBS also has good high-temperature resistance.

[0188] In addition, the higher the mass fraction of SEBS and the larger the weight-average molecular weight, the greater the impact on the coating effect of the bonding adhesive.

[0189] It should be noted that the present application also tested the film thickness data during construction at different spin coating speeds when bonding the bonding adhesive prepared in Example 4 with the wafer. The test results are shown in Table 3 below.

[0190] Table 3

[0191] Spin Coating Speed 1000 rpm 1500 rpm 2000 rpm 2500 rpm 3000 rpm MAX 39.81 25.406 18.241 14.613 11.842 MIN 37.211 23.091 16.141 12.654 10.104 AVE 38.613 24.042 17.001 13.443 11.031 U％ 3.01 2.828 2.632 2.532 2.513 TTV 2.598 2.315 2.1 1.959 1.738

[0192] Among them, MAX represents the maximum film thickness after wafer bonding, MIN represents the minimum film thickness after wafer bonding, AVE represents the average film thickness after wafer bonding, U% is the uniformity, and TTV is the consistency of the film thickness. In addition, the data unit in Table 1 is μm.

[0193] As can be seen from Table 3: at different spin coating speeds, the relevant parameters of the bonding adhesive meet the requirements, that is, at different required thicknesses, the bonding adhesive can meet the usage requirements.

[0194] In summary, the bonding adhesive of the present application combines excellent bonding performance with efficient thermal debonding ability. This integrated design enables the wafer to meet the high-temperature process requirements during processing, significantly improving the coherence of the production process and the adaptability of the process. This design is relatively innovative in the current bonding adhesive technology field, bringing broader application potential and operational convenience to the wafer processing technology.

[0195] Moreover, the present application selects SEBS and rosin modified resin as the main materials of the bonding adhesive. These materials not only exhibit excellent heat resistance and can remain stable in high-temperature environments, but also possess excellent chemical resistance and can resist the erosion of various chemical solvents. This high-temperature stability and chemical resistance make the bonding adhesive more reliable during high-temperature wafer processing, effectively solving the limitations of existing bonding adhesives in high-temperature debonding.

[0196] The above description is only for the convenience of those skilled in the art to understand the technical solution of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A bonding adhesive, characterized in that, The bonding adhesive comprises the following components in parts by mass: 10 - 30 parts of styrene-ethylene-butene-styrene block copolymer, 20 - 40 parts of rosin modified resin, 0.1 - 10 parts of leveling agent, 40 - 70 parts of solvent; Among them, the styrene-ethylene-butene-styrene block copolymer is a linear triblock copolymer with polystyrene as the end segment and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic segment.

2. The bonding adhesive according to claim 1, wherein, The mass ratio of the styrene-ethylene-butene-styrene block copolymer to the rosin modified resin is 0.25 - 1.

5.

3. The bonding adhesive according to claim 1, wherein In the styrene-ethylene-butene-styrene block copolymer, the styrene / rubber ratio is 30% - 67%, and the diblock content is 0.5% - 32%.

4. The bonding adhesive according to claim 1, wherein The weight-average molecular weight range of the styrene-ethylene-butene-styrene block copolymer is 150,000 - 400,000 g / mol.

5. The bonding adhesive according to claim 1, wherein The rosin modified resin includes at least one of rosin modified phenolic resin, rosin modified maleic resin, hydrogenated rosin, and rosin modified polyurethane.

6. The bonding adhesive according to claim 5, wherein The weight-average molecular weight range of the rosin modified resin is 750 - 2500 g / mol.

7. The bonding adhesive according to claim 1, characterized in that, The leveling agent includes at least one of Tech-2046, MF-AX 50S, Glide-450, and WE-D8900N.

8. The bonding adhesive according to claim 1, wherein The solvent includes at least one of toluene, butyl acetate, cyclohexane, isobutyl acetate, n-butyl acetate, xylene, n-octane, decahydronaphthalene, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

9. A method for preparing the bonding adhesive according to any one of claims 1 to 8, characterized in that, The preparation method includes: According to the parts by mass of each component, the solvent and the leveling agent are mixed evenly to obtain a mixed solution; The rosin modified resin is added to the mixed solution and mixed evenly to obtain a precursor; The precursor is heated to 40 - 50 °C, and the styrene-ethylene-butene-styrene block copolymer is added, and stirred until a clear and transparent liquid is formed to obtain the bonding adhesive.

10. Use of the bonding adhesive according to any one of claims 1 to 8 in wafer processing.

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