Adhesive for quartz product as well as preparation method and use method of adhesive

Abstract

The invention provides an adhesive for a quartz product as well as a preparation method and a use method of the adhesive. The adhesive comprises the following components in percentage by weight: 10-30% of glass powder, 55-70% of silica sol, 2-8% of silicate, 10-20% of a thickening agent, 1-5% of a dispersing agent and 1-5% of a room temperature curing agent. Wherein rare earth elements are added into the glass powder. The adhesive not only has an extremely low thermal expansion coefficient, but also has better thermal shock resistance, excellent chemical stability and good corrosion resistance, a more complex network structure can be formed in the adhesive by doping rare earth elements, and a certain shape memory function exists while the stability is improved. The adhesive is applied to the quartz product, can tolerate a high-temperature environment, provides higher shear strength, has a certain self-repairing function, can effectively prolong the service life of the quartz product, and reduces the production cost and the maintenance cost.

Description

Technical Field

[0001] The present invention relates to the technical field of bonding materials, and in particular to an adhesive for quartz products and a preparation method and a use method thereof. Background Art

[0002] In existing semiconductor processing, quartz boats and quartz boat holders are commonly used to transport silicon wafers. Currently, these boats and quartz boat holders are mostly manufactured by welding, which results in high production costs. Furthermore, due to the brittleness of quartz, they are easily bumped or damaged during processing, which is difficult to repair, further increasing costs.

[0003] Currently, quartz adhesives are available that can operate at high temperatures and have a low coefficient of thermal expansion, meeting the requirements of most quartz products. However, semiconductor processing experiences repeated temperature fluctuations, and the deposition process occurs under low pressure, using a large amount of chemical gases. These can deposit various chemical compounds on the surfaces of the quartz boat and adhesive, potentially corroding the adhesive or causing it to age and lose its adhesive properties, thereby reducing its performance and damaging the quartz product. Summary of the Invention

[0004] The purpose of the present invention is to address the shortcomings of the prior art and to propose an adhesive for quartz products, a preparation method thereof, and a use method thereof. The adhesive uses glass powder added with rare earth elements, can withstand high temperature environments, not only has an extremely low thermal expansion coefficient, but also has good thermal shock resistance, excellent chemical stability and good corrosion resistance. The addition of rare earth elements can form a more complex network structure inside the adhesive, increasing stability while having a certain shape memory function. When suffering minor damage, it can slowly self-repair by heating. It can perfectly match the high temperature environment of quartz products in the semiconductor processing process, extend the service life of quartz products, and significantly reduce production costs and maintenance costs.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] According to a first aspect of the present invention, an adhesive for quartz products is provided, comprising the following components by weight: glass powder: 10% to 30%, silica sol: 55% to 70%, silicate: 2% to 8%, thickener: 10% to 20%, dispersant: 1% to 5%, and room temperature curing agent: 1% to 5%.

[0007] Preferably, the glass powder includes the following components in weight fractions: silicon oxide: 50% to 70%, aluminum oxide: 10% to 15%, zinc oxide: 3% to 10%, tellurium oxide: 0% to 5%, alkaline earth metal oxide: 3% to 12%, boron oxide: 1% to 5%, zirconium oxide: 0% to 5%, cerium oxide: 0% to 10%, lanthanum oxide: 0% to 10%, and yttrium oxide: 0% to 10%.

[0008] Preferably, the method for preparing the glass powder comprises:

[0009] Step S1-1: weighing raw materials in proportion;

[0010] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0011] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 to 5 hours to completely melt the material;

[0012] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0013] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0014] Preferably, the average particle size of the glass powder is 1 to 5 μm.

[0015] Preferably, the silica sol has a solid content of 20-30%, an average particle size of 10-20 nm, and a particle dispersion index of less than 0.2.

[0016] Preferably, the silicate is one or both of sodium silicate and potassium silicate.

[0017] Preferably, the thickener is one or both of carboxymethyl cellulose and sodium carboxymethyl cellulose.

[0018] Preferably, the dispersant is sodium polyacrylate.

[0019] Preferably, the room temperature curing agent includes one or both of benzoyl peroxide and azobisisobutyronitrile.

[0020] According to a second aspect of the present invention, there is provided a method for preparing the adhesive for quartz products as described above, the method comprising the following steps:

[0021] Step S2-1: weighing raw materials in proportion;

[0022] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 20 to 30 minutes to prepare a first mixture;

[0023] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0024] Step S2-4: adding a room temperature curing agent to the second mixture and stirring for 60 to 120 minutes to obtain an adhesive.

[0025] According to a third aspect of the present invention, there is provided a method for using the adhesive for quartz products as described above, the method comprising the following steps:

[0026] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 20 to 40 minutes to allow the adhesive to cure, thus completing the initial bonding;

[0027] Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 900-1100°C at a rate of 8-15°C / min, and hold it for 120-240 minutes to allow the adhesive to sinter and bond to the quartz product.

[0028] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0029] Compared with the prior art, the present invention offers the following advantages: When applied to quartz products, the silica in the silica sol forms a silicon-oxygen network through a polycondensation reaction, providing high tensile bond strength. The components of the glass frit work synergistically, not only matching the thermal expansion coefficient of the quartz substrate and reducing interfacial thermal stress, but also enhancing heat resistance and chemical stability through the incorporation of rare earth elements. These elements interact with the silicon-oxygen bonds in the adhesive, enhancing bonding strength and stability while also exhibiting a certain shape memory property. Consequently, the adhesive possesses a thermal expansion coefficient that matches that of the quartz substrate, excellent thermal shock resistance, good corrosion resistance, and a certain degree of self-healing properties, making it suitable for the operating environments of quartz products in semiconductor processing, extending the service life of quartz products. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The present invention is a flow chart of the method for preparing the glass powder.

[0031] Figure 2 The present invention is a flow chart of a method for preparing an adhesive for quartz products.

[0032] Figure 3 The present invention is a flowchart of a method for using an adhesive for quartz products. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings of the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. It is understood that in the absence of conflict, some technical means of the various embodiments described herein can be replaced or combined with each other.

[0034] In the description of the present invention, the terms "first," "second," etc., if used, are used solely to distinguish the objects being described and do not convey any order or technical meaning. Therefore, a term defined as "first," "second," etc. may explicitly or implicitly include one or more of such objects. Furthermore, "a," "an," and similar terms do not denote a limitation on quantity, but rather indicate the presence of at least one, and "plurality" means at least two.

[0035] In the description of the present invention, reference to "one embodiment" or "some embodiments" means that the particular features, structures, or characteristics described in conjunction with the embodiment are included in one or more embodiments of the present invention. Therefore, the phrases "in one embodiment," "in some embodiments," "in other embodiments," "in further embodiments," etc., appearing in different places in this specification do not necessarily refer to the same embodiment, but rather mean "one or more but not all embodiments," unless otherwise specifically emphasized.

[0036] According to a first aspect of the present invention, an adhesive for quartz products is provided, comprising the following components by weight: glass powder: 10% to 30%, silica sol: 55% to 70%, silicate: 2% to 8%, thickener: 10% to 20%, dispersant: 1% to 5%, and room temperature curing agent: 1% to 5%.

[0037] One or more of cerium oxide (CeO2), lanthanum oxide (La2O3), and yttrium oxide (Y2O3) are added to the glass frit. In some embodiments, the weight of lanthanum oxide is 0-3 times the weight of cerium oxide, and the weight of yttrium oxide is 0-3 times the weight of cerium oxide. More preferably, the weight ratio of cerium oxide, lanthanum oxide, and yttrium oxide is 1:1:1.

[0038] The preparation method of the above-mentioned adhesive includes: weighing raw materials in proportion; adding glass powder and silicate to silica sol, then adding a dispersant to fully dissolve, and stirring for 20 to 30 minutes to obtain a first mixture; adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture; adding a room temperature curing agent to the second mixture, stirring for 60 to 120 minutes to obtain an adhesive.

[0039] When the above adhesive is used in the bonding operation of quartz products, first, the adhesive is applied to the bonding surface of the quartz products to be bonded, the bonding surfaces are placed together, and the products are left to stand for 20 to 40 minutes to allow the adhesive to cure and complete the initial bonding; then, the quartz products after the initial bonding are sent to a high-temperature furnace, heated to 900 to 1100°C at a heating rate of 8 to 15°C / minute, and kept at this temperature for 120 to 240 minutes to allow the adhesive to sinter and form a bond with the quartz products; finally, the quartz products are removed from the high-temperature furnace and cooled to room temperature.

[0040] In this adhesive, the silica components of the silica sol and glass frit chemically bond to the quartz substrate, while the dispersant and thickener ensure a homogeneous structure, collectively achieving high bonding strength. Furthermore, the glass frit modulates the coefficient of thermal expansion (CTE) and stabilizes the glass phase structure, while the silica sol network provides high-temperature stability, synergistically resisting stress cracking caused by sudden temperature changes. As a result, this adhesive exhibits an extremely low CTE, along with good thermal shock resistance, excellent chemical stability, and good corrosion resistance. This makes it suitable for the operating environments of quartz products in semiconductor processing, extending their service life while reducing production costs.

[0041] Specifically, silica sol is a colloidal solution of nano-sized silica particles dispersed in water or a solvent. Upon curing, it forms a silica network, providing excellent adhesion and high-temperature resistance. The high silica sol content (55% to 70%) means that the adhesive forms a dense three-dimensional network structure upon curing. Its chemical similarity to the quartz substrate allows the two to be tightly bonded through chemical bonds, ensuring high bonding strength. The high melting point of silica (approximately 1700°C) imparts excellent high-temperature resistance to the adhesive, enabling it to resist structural damage from thermal shock. Furthermore, the high silica sol content ensures that the thermal expansion coefficients of the adhesive and quartz match, reducing thermal mismatch stress.

[0042] Glass frit enhances temperature resistance through a silica-oxygen network, matching the thermal expansion coefficient of the quartz substrate and reducing interfacial thermal stress. The rare earth elements in the glass frit interact with the silica-oxygen bonds on the surface of the quartz substrate, forming a transition layer through chemical bonding. This strengthens the bond between the adhesive and the quartz substrate, achieving interfacial reinforcement. It also enhances the adhesive's antioxidant properties and chemical stability, making it more resistant to high temperatures and chemical corrosion. Thickeners adjust the adhesive's rheological properties, ensuring uniform application during application and avoiding stress concentrations caused by localized thickness variations. They also inhibit component sedimentation during curing, maintaining structural uniformity and reducing weak interfaces caused by component segregation. Dispersants prevent glass frit particle agglomeration, ensuring even distribution of components and forming a homogeneous cured structure, avoiding localized weaknesses. They also enhance the adhesive's storage stability, preventing delamination or precipitation that could affect performance. Room-temperature curing agents promote the gelation of the silica sol and the cross-linking reaction of the system, forming a high-density crosslink network and increasing the stiffness and strength of the adhesive layer.

[0043] After testing, the adhesive was found to provide a shear strength of more than 9 MPa when applied to quartz products, exhibiting good bonding properties. It also performed well in heat shock resistance tests, maintaining a shear strength of more than 6 MPa after 10 rounds of 200°C to 800°C cyclic heat shock tests.

[0044] In some preferred embodiments, the adhesive for quartz products includes the following components in weight fractions: glass powder: 20% to 25%, silica sol: 60% to 65%, silicate: 5% to 6%, thickener: 12% to 15%, dispersant: 2% to 3%, and room temperature curing agent: 3% to 4%.

[0045] In some preferred embodiments, the glass frit comprises the following components by weight: silicon oxide (SiO2): 50%-70%, aluminum oxide (Al2O3): 10%-15%, zinc oxide (ZnO): 3%-10%, tellurium oxide: 0%-5%, alkaline earth metal oxide: 3%-12%, boron oxide (B2O3): 1%-5%, zirconium oxide (ZrO2): 0%-5%, cerium oxide (CeO2): 0%-10%, lanthanum oxide (La2O3): 0%-10%, and yttrium oxide (Y2O3): 0%-10%. Tellurium oxide is preferably tellurium dioxide (TeO2), whose core function is to adjust the thermal expansion coefficient and high-temperature stability of the glass phase, ensuring compatibility between the adhesive and the quartz substrate under thermal shock. Alkaline earth metal oxides can be one or more of barium oxide (BaO), magnesium oxide (MgO), and calcium oxide (CaO).

[0046] In the above-mentioned glass powder, silicon oxide is the main component, which is chemically compatible with the quartz substrate (SiO2), forms a strong interface bond through silicon-oxygen bonds, and improves the bonding strength. Aluminum oxide can increase the hardness and high temperature resistance of the glass phase, enhance the chemical stability and mechanical properties of the adhesive, inhibit high-temperature softening, and reduce deformation under thermal stress. Zinc oxide can be used as a flux to reduce the melting temperature of the glass powder, promote its fluidity during solidification, and improve the wetting of the quartz surface. Boron oxide and silicon oxide synergistically participate in the formation of the glass network structure, which helps to accurately control the thermal expansion coefficient of the glass powder so that it matches the thermal expansion coefficient of the quartz substrate, reduce the interfacial stress caused by temperature changes, and improve the compatibility and durability of the adhesive under thermal shock. Boron oxide interacts with alkaline earth metal oxides, aluminum oxide, etc. to adjust the mechanical strength of the glass. Barium oxide is used to adjust the thermal expansion coefficient to make it closer to quartz (low CTE, about 0.5×10 -6 / K), reducing interfacial stress caused by temperature changes. Tellurium oxide can optimize the glass network structure, enhance high-temperature stability, and assist in adjusting CTE. Alkaline earth metal oxides (such as CaO and MgO) can stabilize the glass structure, improve heat resistance, and inhibit phase separation at high temperatures. Cerium oxide has a unique electronic structure that can interact with the silicon-oxygen bonds on the quartz surface, forming a transition layer through chemical bonding, thereby enhancing the bonding strength between the adhesive and the quartz glass, while improving the adhesive's antioxidant properties and making the adhesive more resistant to high temperatures; yttrium oxide can enable the adhesive to form a more uniform and dense network structure during the curing process, which can improve the mechanical properties of the adhesive and increase the contact area and bonding strength with the quartz glass, thereby enhancing the bonding strength of the adhesive. In addition, yttrium can also adjust the thermal expansion coefficient of the adhesive to a certain extent, reducing the internal stress caused by thermal expansion differences; lanthanum oxide can improve the chemical stability of the adhesive, enhance its corrosion resistance, and protect the bonding interface from erosion.

[0047] Yttrium enables the adhesive to form a more uniform and dense network structure during the curing process, improving its mechanical properties and increasing the contact area and bonding strength with the quartz glass, thereby enhancing the adhesive's bond strength. Yttrium also modulates the adhesive's thermal expansion coefficient to a certain extent, reducing internal stress caused by differential thermal expansion. Lanthanum improves the adhesive's chemical stability, enhancing its corrosion resistance and protecting the bonding interface from erosion. Cerium, with its unique electronic structure, interacts with the silicon-oxygen bonds on the quartz surface, forming a transition layer through chemical bonding, strengthening the adhesive's bond to the quartz glass and enhancing its antioxidant properties, resulting in improved high-temperature resistance. By adjusting the ratio of Y2O3, La2O3, and CeO2, precise matching of the adhesive's thermal expansion coefficient, high-temperature phase stability, multi-mechanism interface strengthening, and cross-scale optimization of thermal shock resistance can be achieved.

[0048] Specifically, La 3+ Larger ionic radius It can significantly reduce the thermal expansion coefficient of the glass phase. It forms [LaO6] polyhedrons with silicon dioxide, which can inhibit the high-temperature expansion of the silicon-oxygen network. 3+ Small ionic radius After introduction, it can form a more compact [YO4] tetrahedron, and cooperate with La2O3 to adjust the thermal expansion coefficient gradient, making the overall thermal expansion coefficient of the adhesive closer to that of quartz. 4+ / Ce 3+ The variable valence property locally adjusts the oxygen vacancy concentration, dynamically compensating for thermal expansion fluctuations caused by temperature changes. The three functions synergistically to ensure a dynamic balance in the thermal expansion coefficient.

[0049] Y 3+ and La 3+ The formation of double rare earth ion barrier in the glass phase can inhibit the depolymerization of silicon-oxygen chains at high temperature and increase the softening point of glass from 800℃ to above 950℃. 4+ →Ce 3+ The reduction reaction absorbs oxygen free radicals, preventing the adhesive layer from becoming brittle due to oxidation. The synergistic combination of yttrium oxide, lanthanum oxide, and cerium oxide enables the adhesive to retain >85% of its bond strength after aging at 1000°C for 24 hours, achieving a synergistic enhancement of high-temperature phase stability.

[0050] In terms of strengthening interface bonding, La 3+ It preferentially adsorbs on the defects of the quartz surface and forms La-O-Si bonds with silicon dioxide; Y 3+ CeO2 nanoparticles (especially partially reduced Ce2O3) can fill the nano-scale pores on the quartz surface and form a mechanical interlocking structure. 3+ The excess positive charge neutralizes the Si-O-groups on the quartz surface, reducing interfacial electrostatic repulsion and promoting wetting.

[0051] In some embodiments, the glass powder includes the following components in weight fractions: silicon oxide (SiO2): 50% to 70%, aluminum oxide (Al2O3): 10% to 15%, zinc oxide (ZnO): 5% to 10%, tellurium dioxide (TeO2): 3% to 5%, barium oxide (BaO): 5% to 8%, boron oxide (B2O3): 1% to 5%, zirconium oxide (ZrO2): 3% to 5%, cerium oxide (CeO2): 2% to 10%, lanthanum oxide (La2O3): 2% to 10%, and yttrium oxide (Y2O3): 2% to 10%.

[0052] Further, refer to Figure 1 The preparation method of the glass powder comprises:

[0053] Step S1-1: weighing raw materials in proportion;

[0054] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0055] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 to 5 hours to completely melt the material;

[0056] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0057] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0058] In some preferred embodiments, the average particle size of the glass powder is 1 to 5 μm, which ensures that the glass powder has a large specific surface area, can improve the bonding strength between the glass powder and other components, and enhance the density and impact resistance of the adhesive.

[0059] In some preferred embodiments, the solid content of the silica sol (the weight fraction of silicon dioxide in the solution) is 20-30%, the average particle size is 10-20 nm, and the particle dispersion index (PDI) is less than 0.2.

[0060] The moderate solid content in the silica sol ensures sufficient silica nanoparticle loading to form a dense network while avoiding the difficulty of coating due to excessive viscosity of the system. The three-dimensional network structure formed after curing is more complete and the mechanical strength is significantly improved. It can also reduce the volume shrinkage caused by water volatilization during the curing process, reduce interfacial stress, and prevent cracking or debonding of the adhesive layer. The specific surface area of ​​nano-particles is about 100 to 300 m 2 / g, fully penetrating the microscopic pores on the quartz substrate surface, creating a mechanical anchoring effect and enhancing interfacial bonding. The high surface activity of the nanoparticles promotes synergistic sintering with glass powder and rare earth elements, forming a uniform "glass-nanoceramic" composite structure in microscopic areas and enhancing thermal shock resistance. Excellent particle monodispersity avoids localized accumulation or defects caused by a wide particle size distribution, ensuring a uniform cured layer structure and stable mechanical properties.

[0061] In some preferred embodiments, the silicate is one or both of sodium silicate and potassium silicate. Silicate has excellent bonding properties, and it can synergize with silica sol to form a denser silica network structure, significantly improving the bonding strength and mechanical properties of the adhesive. The alkaline environment of the silicate can adjust the pH of the system, promote the gelation process of the silica sol, and dissolve some components in the glass powder (such as silicon oxide or metal oxide), releasing active ions to participate in the reaction, thereby enhancing the structural stability after curing. During the curing process, silicate forms water-insoluble silicon-oxygen bonds (Si-O-Si), giving the adhesive good water resistance and chemical corrosion resistance. In addition, after drying or curing, the silicate forms a glassy matrix, filling the pores in the adhesive layer, reducing stress concentration, and thus improving the impact resistance and durability of the adhesive.

[0062] In some preferred embodiments, the thickener is one or both of carboxymethyl cellulose and sodium carboxymethyl cellulose. The thickener is used to adjust the rheological properties of the adhesive, ensuring uniform application during application and avoiding stress concentration caused by localized thickness variations. Furthermore, the thickener can inhibit component sedimentation during the curing process, maintaining structural uniformity and reducing weak interfaces caused by component segregation.

[0063] In some preferred embodiments, the dispersant is sodium polyacrylate. Dispersants can prevent agglomeration of particles such as glass powder and rare earth element additives, ensuring even distribution of components and forming a homogeneous cured structure, avoiding localized weaknesses. Dispersants can also improve the storage stability of the adhesive, preventing delamination or precipitation that could affect performance.

[0064] In some preferred embodiments, the room temperature curing agent includes one or both of benzoyl peroxide and azobisisobutyronitrile. The room temperature curing agent is used to promote the gelation of the silica sol and the cross-linking reaction of the system, forming a high cross-linking density network, and improving the rigidity and strength of the adhesive layer.

[0065] According to a second aspect of the present invention, a method for preparing the adhesive for quartz products as described above is provided, referring to Figure 2 , the preparation method comprises the following steps:

[0066] Step S2-1: weighing raw materials in proportion; wherein the weight fraction of each component is: glass powder: 10% to 30%, silica sol: 55% to 70%, silicate: 2% to 8%, thickener: 10% to 20%, dispersant: 1% to 5%, room temperature curing agent: 1% to 5%.

[0067] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 20 to 30 minutes to prepare a first mixture;

[0068] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0069] Step S2-4: adding a room temperature curing agent to the second mixture and stirring for 60 to 120 minutes to obtain an adhesive.

[0070] In the above preparation method, the raw materials are mixed in stages and kept warm continuously to ensure that the glass powder is fully dissolved in the silica sol and to avoid gelation of the silica sol caused by high temperature; the dispersant and mechanical stirring work synergistically to significantly improve the dispersion of the glass powder in the silica sol, reduce interface defects, and improve the density and shear strength of the bonding layer.

[0071] The adhesive prepared by the above method is applied to quartz products. The silica sol forms a silicon-oxygen network through a condensation reaction, providing high tensile bonding strength; the glass powder enhances temperature resistance through the silicon-oxygen network, matches the thermal expansion coefficient of the quartz matrix, and reduces interfacial thermal stress; the rare earth elements interact with the silicon-oxygen bonds on the surface of the quartz matrix, forming a transition layer through chemical bonding, thereby enhancing the bonding force between the adhesive and the quartz matrix; the adhesive has an extremely low thermal expansion coefficient, good thermal shock resistance, excellent chemical stability and good corrosion resistance, can match the use environment of quartz products in the semiconductor processing process, and extend the service life of the quartz products.

[0072] According to a third aspect of the present invention, a method for using the adhesive for quartz products as described above is provided, referring to Figure 3 , the method of use includes the following steps:

[0073] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, place the surfaces together, and allow the adhesive to cure for 20-40 minutes, completing the initial bonding. This step allows for quick positioning of the quartz products, facilitating operation and temporary fixation.

[0074] Step S3-2: The quartz product after preliminary bonding is sent into a high-temperature furnace, heated to 900-1100°C at a heating rate of 8-15°C / minute, and kept warm for 120-240 minutes to allow the adhesive to sinter and bond with the quartz product. Controlling the heating rate to 8-15°C / minute can balance the release of thermal stress and the sintering efficiency, and prevent the quartz product from breaking due to sudden heat. The sintering temperature is 900-1100°C, and the insulation stage is controlled to 120-240 minutes to ensure that the interface reaction between the adhesive and quartz is fully completed, making the interface structure densified. After high-temperature sintering and curing, the glass phase and the quartz matrix form chemical bonds through diffusion bonding, which significantly improves the final bonding strength. At the same time, the adhesive layer after high-temperature sintering is an inorganic system, which avoids the pollution problem caused by high-temperature decomposition of organic adhesives.

[0075] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0076] The present invention significantly improves the reliability and life of quartz products in extreme environments through an inorganic-rare earth composite system and a step-by-step curing process, reduces production costs, and achieves environmental protection goals, thus having clear industrial application value.

[0077] The following is a comparative analysis of the effects of different adhesive components or processes on the performance of quartz products through four embodiments of the present invention and four comparative examples.

[0078] Table 1 below shows the weight ratios of the adhesive components in Examples 1-4 of the present invention and Comparative Examples 2-3.

[0079] Table 1

[0080] Adhesive components Example 1 Example 2 Example 3 Example 4 Comparative Example 2 Comparative Example 3 Glass powder 1 15％ 20％ / / / / Glass powder 2 / / 15％ 20％ / / Comparative example glass powder / / / / 15％ 20％ Silica Sol 65％ 58％ 65％ 58％ 65％ 58％ Sodium silicate 2.5％ 2.5％ 2.5％ 2.5％ 2.5％ 2.5％ Potassium silicate 2.5％ 2.5％ 2.5％ 2.5％ 2.5％ 2.5％ thickener 11％ 11％ 11％ 11％ 11％ 11％ dispersants 2％ 4％ 2％ 4％ 2％ 4％ Room temperature curing agent 2％ 2％ 2％ 2％ 2％ 2％ sum 100％ 100％ 100％ 100％ 100％ 100％

[0081] Table 2 below shows the weight ratios of the components of the glass frit 1 used in Examples 1-2, the glass frit 2 used in Examples 3-4, and the comparative example glass frit used in Comparative Examples 2-3.

[0082] Table 2

[0083]

[0084]

[0085] The test results of shear strength and service life of the quartz products in the four embodiments and four comparative examples are shown in Table 3.

[0086] Table 3

[0087]

[0088] Example 1:

[0089] The adhesive comprises the following components by weight: glass frit 1:15%, silica sol: 65%, silicate: 5%, thickener: 11%, dispersant: 2%, and room temperature curing agent: 2%. The silicate comprises sodium silicate: 2.5% and potassium silicate: 2.5%. Sodium carboxymethyl cellulose is used as the thickener.

[0090] The glass powder 1 includes the following components in weight fractions: silicon oxide: 60%, aluminum oxide: 12%, zinc oxide: 5%, barium oxide: 5%, boron oxide: 2%, zirconium oxide: 4%, cerium oxide: 4%, lanthanum oxide: 4%, and yttrium oxide: 4%.

[0091] The preparation method of the glass powder 1 comprises:

[0092] Step S1-1: weighing raw materials in proportion;

[0093] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0094] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 hours to completely melt the material;

[0095] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0096] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0097] The preparation method of the adhesive comprises:

[0098] Step S2-1: Weighing the raw materials of the adhesive according to proportion;

[0099] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 30 minutes to prepare a first mixture;

[0100] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0101] Step S2-4: Add a room temperature curing agent to the second mixture and stir for 60 minutes to obtain an adhesive.

[0102] The use of this adhesive includes:

[0103] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 30 minutes to allow the adhesive to cure, thus completing the initial bonding;

[0104] Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 950°C at a rate of 10°C / min, and hold it for 180 minutes to allow the adhesive to sinter and bond to the quartz product;

[0105] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0106] In adhesive materials, shear strength is commonly used to measure a material's resistance to shear failure. Shear strength refers to the maximum shear stress a material or object can withstand when subjected to a shear force. The shear strength test method used in this article follows the test protocol outlined in national standard GB / T 7124-2008. A tensile force is applied parallel to the bonding surface and in the direction of the principal axis, and the shear stress at the lap joint is measured. Testing has shown that this adhesive provides a shear strength exceeding 7.3 MPa, demonstrating excellent bonding performance. It also performs well in thermal shock resistance tests, maintaining a shear strength of over 6.0 MPa after 10 cycles of thermal shock testing at 200°C to 800°C, demonstrating its adaptability to the working environment. Testing has shown that quartz boats produced using this method have an average service life of 198 days in semiconductor processing, compared to the average service life of quartz boats produced using welding processes, which is generally around 240 days. Therefore, the adhesive of this invention, when used in quartz products for the semiconductor industry, can achieve a lifespan comparable to that of quartz tubes produced using welding processes, while offering lower production costs and easier repair.

[0107] Example 2:

[0108] The adhesive comprises the following components by weight: glass frit 1: 20%, silica sol: 58%, silicate: 5%, thickener: 11%, dispersant: 4%, and room temperature curing agent: 2%. The silicate comprises sodium silicate: 2.5% and potassium silicate: 2.5%. The thickener is sodium carboxymethyl cellulose.

[0109] The glass powder 1 includes the following components in weight fractions: silicon oxide: 60%, aluminum oxide: 12%, zinc oxide: 5%, barium oxide: 5%, boron oxide: 2%, zirconium oxide: 4%, cerium oxide: 4%, lanthanum oxide: 4%, and yttrium oxide: 4%.

[0110] The preparation method of the glass powder 1 comprises:

[0111] Step S1-1: weighing raw materials in proportion;

[0112] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0113] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 hours to completely melt the material;

[0114] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0115] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0116] The preparation method of the adhesive comprises:

[0117] Step S2-1: Weighing the raw materials of the adhesive according to proportion;

[0118] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 30 minutes to prepare a first mixture;

[0119] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0120] Step S2-4: Add a room temperature curing agent to the second mixture and stir for 60 minutes to obtain an adhesive.

[0121] The use of this adhesive includes:

[0122] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 30 minutes to allow the adhesive to cure, thus completing the initial bonding;

[0123] Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 950°C at a rate of 10°C / min, and hold it for 180 minutes to allow the adhesive to sinter and bond to the quartz product;

[0124] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0125] Compared to Example 1, Example 2 adjusted the ratio of glass frit and silica sol in the adhesive. Testing showed that the adhesive provided a shear strength exceeding 9.3 MPa, demonstrating excellent bonding performance. It also performed well in thermal shock resistance tests, maintaining a shear strength exceeding 7.8 MPa after 10 cycles of thermal shock testing at 200°C to 800°C, demonstrating improved performance compared to Example 1. Testing also demonstrated that quartz boats prepared using this solution had a service life of up to 226 days in semiconductor processing.

[0126] Example 3:

[0127] The adhesive comprises the following components by weight: glass frit 2: 15%, silica sol: 65%, silicate: 5%, thickener: 11%, dispersant: 2%, and room temperature curing agent: 2%. The silicate comprises sodium silicate: 2.5% and potassium silicate: 2.5%. The thickener is sodium carboxymethyl cellulose.

[0128] The glass powder 2 includes the following components in weight fractions: silicon oxide: 52%, aluminum oxide: 12%, zinc oxide: 5%, barium oxide: 5%, boron oxide: 2%, tellurium dioxide: 4%, magnesium oxide: 3%, cerium oxide: 6%, lanthanum oxide: 6%, and yttrium oxide: 5%.

[0129] The preparation method of the glass powder 2 includes:

[0130] Step S1-1: weighing raw materials in proportion;

[0131] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0132] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 hours to completely melt the material;

[0133] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0134] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0135] The preparation method of the adhesive comprises:

[0136] Step S2-1: Weighing the raw materials of the adhesive according to proportion;

[0137] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 30 minutes to prepare a first mixture;

[0138] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0139] Step S2-4: Add a room temperature curing agent to the second mixture and stir for 60 minutes to obtain an adhesive.

[0140] The use of this adhesive includes:

[0141] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 30 minutes to allow the adhesive to cure, thus completing the initial bonding;

[0142] Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 950°C at a rate of 10°C / min, and hold it for 180 minutes to allow the adhesive to sinter and bond to the quartz product;

[0143] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0144] Compared with Example 1, the composition of the glass powder is adjusted in Example 3. After testing, the adhesive can provide a shear strength of more than 7.1 MPa, has good bonding performance, and performs well in the heat shock test. After 10 rounds of 200°C to 800°C cyclic heat shock tests, it still maintains a shear strength of more than 5.7 MPa. After testing, the quartz boat product prepared using this solution can have a service life of up to 188 days in the semiconductor processing technology.

[0145] Example 4:

[0146] The adhesive comprises the following components by weight: glass frit 2: 20%, silica sol: 58%, silicate: 5%, thickener: 11%, dispersant: 4%, and room temperature curing agent: 2%. The silicate comprises sodium silicate: 2.5% and potassium silicate: 2.5%. The thickener is sodium carboxymethyl cellulose.

[0147] The glass powder 2 includes the following components in weight fractions: silicon oxide: 52%, aluminum oxide: 12%, zinc oxide: 5%, barium oxide: 5%, boron oxide: 2%, tellurium dioxide: 4%, magnesium oxide: 3%, cerium oxide: 6%, lanthanum oxide: 6%, and yttrium oxide: 5%.

[0148] The preparation method of the glass powder 2 includes:

[0149] Step S1-1: weighing raw materials in proportion;

[0150] Step S1-2: placing the raw materials into a ball mill and thoroughly milling and mixing;

[0151] Step S1-3: placing the ball-milled and uniformly mixed material into a high-temperature furnace, heating it to above 1200°C, and heating it for 4 hours to completely melt the material;

[0152] Step S1-4: Based on the water quenching principle, the molten glass melt is quickly poured into cold water to cause the glass melt to quickly cool and shrink, breaking into fine glass particles;

[0153] Step S1-5: The glass particles obtained by water quenching are dried and then ground using a ball mill to obtain glass powder of desired fineness.

[0154] The preparation method of the adhesive comprises:

[0155] Step S2-1: Weighing the raw materials of the adhesive according to proportion;

[0156] Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 30 minutes to prepare a first mixture;

[0157] Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture;

[0158] Step S2-4: Add a room temperature curing agent to the second mixture and stir for 60 minutes to obtain an adhesive.

[0159] The use of this adhesive includes:

[0160] Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 30 minutes to allow the adhesive to cure, thus completing the initial bonding;

[0161] Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 950°C at a rate of 10°C / min, and hold it for 180 minutes to allow the adhesive to sinter and bond to the quartz product;

[0162] Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

[0163] Compared to Example 3, Example 4 adjusted the composition ratio of the adhesive raw materials. Testing showed that the adhesive provided a shear strength exceeding 8.8 MPa, demonstrating good bonding performance. It also performed well in thermal shock resistance tests, maintaining a shear strength exceeding 7.5 MPa after 10 cycles of thermal shock testing at 200°C to 800°C. Testing also demonstrated that the quartz boat produced using this solution had a service life of up to 215 days in semiconductor processing.

[0164] Comparative Example 1: Quartz products were produced using a welding process. Tests have shown that the quartz boat product produced using this solution has a service life of up to 240 days in semiconductor processing.

[0165] Comparative Example 2: Only the glass powder formula was adjusted to a glass powder formula without rare earth elements, and the remaining steps and the ratio of adhesive raw materials were consistent with Example 1. After testing, the quartz boat product prepared using this method had a service life of 134 days in semiconductor processing technology.

[0166] Comparative Example 3: Only the glass powder formula was adjusted to a glass powder formula without rare earth elements, and the remaining steps and the ratio of adhesive raw materials were consistent with Example 2. After testing, the quartz boat product prepared using this method had a service life of 129 days in semiconductor processing technology.

[0167] Comparative Example 4: A quartz product was obtained by bonding with an adhesive in the prior art. Testing showed that the service life of the quartz boat product prepared using this solution in semiconductor processing was only 50 days.

[0168] The above data comparison demonstrates that the adhesives of Examples 1-4, when applied to quartz products in the semiconductor field, can achieve a lifespan comparable to that of the quartz tubes produced using the welding process in Comparative Example 1, while offering lower production costs and facilitating self-repair of the quartz products. Compared to Comparative Example 4, the adhesives of Examples 1-4 all demonstrate excellent performance, effectively extending the service life of the quartz tubes. Compared to Comparative Examples 2 and 3, the glass frits of Examples 1-4 all incorporate rare earth elements, enhancing the heat resistance and chemical stability of the quartz products, thereby extending the service life of the quartz products.

[0169] The adhesive of the present invention is applied to quartz products. The silica in the silica sol forms a silicon-oxygen network through a condensation reaction, providing high tensile bond strength. The components of the glass frit work synergistically to not only match the thermal expansion coefficient of the quartz substrate, reducing interfacial thermal stress, but also enhance heat resistance and chemical stability through the incorporation of rare earth elements. These interact with the silicon-oxygen bonds in the adhesive, enhancing bonding strength and stability while also exhibiting a certain shape memory function. As a result, the adhesive has a thermal expansion coefficient that matches that of the quartz substrate, excellent thermal shock resistance, good corrosion resistance, and a certain self-repairing function. This makes it suitable for the use environment of quartz products in semiconductor processing, extending the service life of quartz products.

[0170] The present invention has been described with reference to the above embodiments. However, the above embodiments are merely exemplary embodiments of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the present invention. On the contrary, modifications and improvements that do not depart from the spirit and scope of the present invention are intended to be protected by the present invention.

Claims

1. An adhesive for quartz products, characterized in that: The adhesive for quartz products includes the following components by weight: Glass powder: 10% to 30%; Silica sol: 55% to 70%; Silicate: 2% to 8%; Thickener: 10% to 20%; Dispersant: 1% to 5%; Room temperature curing agent: 1%~5%.

2. The adhesive for quartz products according to claim 1, wherein: The glass powder includes the following components by weight: Silicon oxide: 50% to 70%; Alumina: 10% to 15%; Zinc oxide: 3% to 10%; Tellurium oxide: 0% to 5%; Alkaline earth metal oxides: 3% to 12%; Boron oxide: 1% to 5%; Zirconia: 0% to 5%; Cerium oxide: 0% to 10%; Lanthanum oxide: 0% to 10%; Yttrium oxide: 0%~10%.

3. The adhesive for quartz products according to claim 1, wherein: The average particle size of the glass powder is 1 to 5 μm.

4. The adhesive for quartz products according to claim 1, wherein: The solid content of the silica sol is 20-30%, the average particle size is 10-20 nm, and the particle dispersion index is less than 0.

2.

5. The adhesive for quartz products according to claim 1, wherein: The silicate is one or both of sodium silicate and potassium silicate.

6. The adhesive for quartz products according to claim 1, wherein: The thickener is one or both of carboxymethyl cellulose and sodium carboxymethyl cellulose.

7. The adhesive for quartz products according to claim 1, wherein: The dispersant is sodium polyacrylate.

8. The adhesive for quartz products according to claim 1, wherein: The room temperature curing agent includes one or both of benzoyl peroxide and azobisisobutyronitrile.

9. A method for preparing an adhesive for quartz products according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: Step S2-1: weighing raw materials according to proportion; Step S2-2: adding glass powder and silicate to the silica sol, then adding a dispersant to fully dissolve, and stirring for 20 to 30 minutes to prepare a first mixture; Step S2-3: adding a thickener to the first mixture to adjust the viscosity to obtain a second mixture; Step S2-4: adding a room temperature curing agent to the second mixture and stirring for 60 to 120 minutes to obtain an adhesive.

10. A method for using the adhesive for quartz products according to any one of claims 1 to 8, characterized in that: The method of use comprises the following steps: Step S3-1: Apply adhesive to the bonding surfaces of the quartz products to be bonded, align the bonding surfaces, and let them stand for 20 to 40 minutes to allow the adhesive to cure, thus completing the initial bonding; Step S3-2: Place the preliminarily bonded quartz product into a high-temperature furnace, heat it to 900-1100°C at a rate of 8-15°C / min, and hold it for 120-240 minutes to allow the adhesive to sinter and bond to the quartz product. Step S3-3: Take the quartz product out of the high-temperature furnace and cool it to room temperature.

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