Borosilicate glass as well as preparation method and application thereof

Abstract

The invention provides borosilicate glass as well as a preparation method and application thereof. The borosilicate glass is prepared from the following components in percentage by mass: 60 percent to 75 percent of SiO2, 10 percent to 18 percent of B2O3, 4 percent to 8 percent of Al2O3, 1 percent to 5 percent of MgO, 4 percent to 9 percent of CaO, 0.5 percent to 2 percent of P2O5, 0.2 percent to 2 percent of ZnO, 0.3 percent to 1.5 percent of Ta2O5 and 0.1 percent to 1 percent of Sc2O3. The borosilicate glass provided by the invention has excellent thermal properties, surface properties, dielectric properties, processability and optical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass, in particular to a borosilicate glass and a preparation method and application thereof. BACKGROUND

[0002] With the increasing requirements of high-performance computing (HPC), artificial intelligence (AI) chips and 5G / 6G communication devices on integration density and heat dissipation performance, the traditional organic substrate has reached the physical limit; its thermal stability and dimensional stability and other performances have obvious deficiencies, and it is difficult to meet the packaging requirements of the next generation of chips. Glass substrates have excellent thermal stability, ultra-low thermal expansion coefficient, and controllability, excellent mechanical stiffness, and gradually become the best material to replace organic substrates.

[0003] However, the thermal expansion coefficient and bonding strength of the traditional glass substrate still have certain deficiencies, and it is difficult to match the silicon chip, so further improvement is needed. SUMMARY

[0004] Therefore, one or more embodiments of the present application provide a borosilicate glass with a thermal expansion coefficient matching a silicon chip, high surface bonding strength, low dielectric coefficient and high ultraviolet transmittance, and a preparation method and application thereof.

[0005] According to a first aspect of an embodiment of the present application, a borosilicate glass is provided, which includes the following components in terms of mass percentage: SiO2 60%~75%, B2O3 10%~18%, Al2O3 4%~8%, MgO 1%~5%, CaO 4%~9%, P2O5 0.5%~2%, ZnO 0.2%~2%, Ta2O5 0.3%~1.5% and Sc2O3 0.1%~1%.

[0006] In some embodiments, the borosilicate glass includes the following components in terms of mass percentage: SiO2 65%~70%, B2O3 12%~16%, Al2O3 5%~7%, MgO 2%~4%, CaO 5%~8%, P2O5 0.8%~1.5%, ZnO 0.5%~1%, Ta2O5 0.6%~1% and Sc2O3 0.2%~0.6%.

[0007] In some embodiments, the components of the borosilicate glass further include 0.05%~0.2% of a fining agent in terms of mass percentage.

[0008] Optionally, the fining agent includes one or more of NaCl and CeO2.

[0009] In some embodiments, the borosilicate glass satisfies at least one of the following characteristics:

[0010] (1) the coefficient of thermal expansion of the borosilicate glass is ≤ 55 x 10 -7 / ℃;

[0011] (2) the dielectric constant of the borosilicate glass is ≤ 5 at 10 GHz;

[0012] (3) the dielectric loss of the borosilicate glass is ≤ 8.1 x 10 -3 at 10 GHz.

[0013] According to a second aspect of the embodiments of the present application, a preparation method of a borosilicate glass is provided, comprising the following steps:

[0014] providing raw materials according to the components of the borosilicate glass as described above to prepare a mixture;

[0015] sequentially performing melting forming and quenching treatment on the mixture to prepare the borosilicate glass.

[0016] In some embodiments, the step of preparing the mixture comprises:

[0017] providing raw materials according to the mass percentages of SiO2, B2O3, Al2O3, MgO, CaO, Ta2O5 and Sc2O3, mixing uniformly to prepare a mixed intermediate material;

[0018] mixing the mixed intermediate material, P2O5 powder and ZnO powder at 1300℃~1500℃ to prepare the mixture.

[0019] In some embodiments, the preparation method of the borosilicate glass satisfies at least one of the following features:

[0020] (1) the temperature of the melting forming is 1550℃~1650℃, and the time is 4h~8h;

[0021] (2) the quenching treatment comprises sequentially performed first quenching treatment and second quenching treatment, the cooling speed of the first quenching treatment is 40℃ / s~60℃ / s, and the cooling speed of the second quenching treatment is 0.5℃ / s~2℃ / s;

[0022] (3) the method of the melting forming comprises one or more of float forming, slot down-draw forming and overflow forming.

[0023] In some embodiments, after the quenching treatment, the step of performing etching treatment on the mixture is further included;

[0024] Optionally, the etching treatment comprises sequentially performed acidic etching treatment and alkaline activation treatment;

[0025] Further optionally, the solution of the acid etching treatment comprises a hydrofluoric acid solution and a sulfuric acid solution.

[0026] Further optionally, the solution of the alkaline activation treatment comprises a sodium hydroxide solution and a cetyltrimethylammonium bromide solution.

[0027] According to a third aspect of the embodiments of the present application, a glass product is provided, comprising the borosilicate glass or the borosilicate glass prepared by the method as described above.

[0028] According to a fourth aspect of the embodiments of the present application, an application of the borosilicate glass or the borosilicate glass prepared by the method as described above in preparing an integrated antenna, an electronic package or a micro-electro-mechanical system package is provided.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] The present application controls the mass percentage of each component of the borosilicate glass, so that each component synergistically acts to precisely control the thermal expansion coefficient of the borosilicate glass. Meanwhile, by adding Ta2O5 and Sc2O3 in the glass component, a tantalum-scandium-rich phase can be formed during heat treatment to improve the bonding strength of the borosilicate glass. Moreover, P 5+ The [PO4] tetrahedron formed by the ions during melting is connected to the [SiO4] network through P-O-Si bonds, which can increase the proportion of bridge oxygen and reduce the ultraviolet absorption group caused by non-bridge oxygen, so that the ultraviolet cutoff wavelength is blue-shifted to below 190 nm, and the transmittance of the borosilicate glass is significantly improved. 2+ It can also effectively block the ion migration channel of alkali metals and alkaline earth metals, thereby reducing the dielectric loss of the borosilicate glass. DETAILED DESCRIPTION

[0031] To make the above objectives, features and advantages of the present application more apparent, the specific embodiments of the present application are described in detail. In the following description, a large number of specific details are set forth in order to fully understand the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited to the specific embodiments disclosed below.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Unless otherwise expressly stated, the various materials, reagents, and equipment and the like to which reference is made in the course of the present application are available from commercial vendors or can be prepared by conventional techniques known to those of skill in the art.

[0033] The selection scope of the terms "and / or", "or / and", "and / or" used herein includes any one of two or more relevant listed items, and also includes any and all combinations of the relevant listed items, which includes any two relevant listed items, any more relevant listed items, or all relevant listed items. It should be noted that when at least two conjunctions selected from "and / or", "or / and", "and / or" are combined to connect at least three items, it should be understood that in the present application, the technical solution undoubtedly includes the technical solution connected by "logical and", and also undoubtedly includes the technical solution connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C and D (i.e. the technical solution connected by "logical or"), and also includes any and all combinations of A, B, C and D, i.e. includes the combination of any two or any three of A, B, C and D, and also includes the four-item combination of A, B, C and D (i.e. the technical solution connected by "logical and").

[0034] In the present application, "multiple", "various", "multiple times", "multiple" and the like are used without specific limitation, which means greater than or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.

[0035] The "combination thereof", "any combination thereof", "any combination manner thereof" and the like used herein include all suitable combination manners of any two or more listed items.

[0036] In the present application, "suitable", "suitable", "any suitable manner" and the like are described in the "suitable" manner, which can implement the technical solutions of the present application, solve the technical problems of the present application, and achieve the expected technical effects of the present application.

[0037] In the present application, "preferably", "better", "better", "preferably" only describe the implementation manner or embodiment with better effect, and it should be understood that it does not constitute a limitation on the protection scope of the present application.

[0038] In the present application, "further", "furthermore", "in particular" and the like are used to describe purposes and represent differences in content, but should not be understood as limiting the scope of protection of the present application.

[0039] In the present application, "optionally", "optional" and "optional" mean optional, i.e. selected from either "yes" or "no" of the two parallel schemes. If there are multiple "options" in a technical solution, and there is no special instruction, and there is no contradiction or mutual restriction, each "option" is independent.

[0040] In the present application, the technical features described in an open manner include both closed technical solutions consisting of listed features and open technical solutions containing listed features.

[0041] In the present application, if no special instruction is given, the numerical value distribution in the above numerical interval is regarded as continuous, and includes the two numerical endpoints (i.e. the minimum value and the maximum value) of the numerical range and every numerical value between the two numerical endpoints. If no special instruction is given, when the numerical interval only points to the integers in the numerical interval, including the two endpoint integers of the numerical range and every integer between the two endpoints, in this article, it is equivalent to directly listing each integer, such as t is an integer selected from 1-10, which means that t is any integer selected from the integer group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. In addition, when multiple ranges are provided to describe characteristics or properties, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all sub-ranges encompassed therein.

[0042] In the present application, the temperature parameter, if not specially limited, allows constant temperature treatment and allows variation within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. It is allowed to fluctuate within the range of ±5℃, ±4℃, ±3℃, ±2℃, ±1℃.

[0043] In the present application, %(w / w) and wt% both represent weight percentage, %(v / v) represents volume percentage, and %(w / v) represents mass volume percentage.

[0044] Some embodiments of the present application provide a borosilicate glass, comprising the following components in mass percentage: SiO2 60%~75%, B2O3 10%~18%, Al2O3 4%~8%, MgO 1%~5%, CaO 4%~9%, P2O5 0.5%~2%, ZnO 0.2%~2%, Ta2O5 0.3%~5%, and Sc2O3 0.1%~1%.

[0045] The present application controls the mass percentage of each component of borosilicate glass, so that each component synergistically acts to precisely control the thermal expansion coefficient of borosilicate glass. Meanwhile, by adding Ta2O5 and Sc2O3 in the glass component, a tantalum-rich scandium phase can be formed during heat treatment, and the bonding strength of borosilicate glass can be improved. Moreover, P 5+ The ions form [PO4] tetrahedron during melting, which is connected with the [SiO4] network through P-O-Si bond, can increase the proportion of bridge oxygen, reduce the ultraviolet absorption group caused by non-bridge oxygen, make the ultraviolet cutoff wavelength blue shift to below 190 nm, and significantly improve the transmittance of borosilicate glass; Zn 2+ It can also effectively block the ion migration channel of alkali metal and alkaline earth metal, thereby reducing the dielectric loss of borosilicate glass.

[0046] SiO2 is a glass-forming oxide, and the irregular continuous network formed by the structural unit of silicon-oxygen tetrahedron is the skeleton of the glass; the dielectric loss of the glass is mainly determined by the tightness of the network structure, the tighter the network structure, the smaller the dielectric loss; if the content of SiO2 is too low, the glass network integrity will be poor, the migration of extraneous ions in the glass will become easy, the ion displacement polarization and the orientation polarization of the polar bond will increase, causing the absorption of electromagnetic signals, the electromagnetic wave transmittance will decrease, the dielectric constant and the dielectric loss will increase, and the thermal expansion coefficient of the glass will increase too much, and the chemical resistance will decrease; if the content of SiO2 is too high, the glass melting and refining temperature will be higher, and the viscosity will increase, which makes it difficult to homogenize the glass, and it is not suitable for glass forming process manufacturing, and the production cost is high.

[0047] For example, the mass percentage of SiO2 can be 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, or any value within the range formed by any two of the above values. Further, the mass percentage of SiO2 is 65% to 70%.

[0048] B2O3 is also a glass-forming oxide, and the boron-oxygen tetrahedron has a framework structure. The tight structure can effectively reduce the absorption and attenuation of electromagnetic signals when passing through the glass substrate, can reduce the thermal expansion coefficient of the glass, and improve the thermal stability, chemical stability and elastic modulus of the glass. At the same time, B2O3 can reduce the glass polarization rate to reduce the dielectric constant and dielectric loss of the glass. If the content of B2O3 is low, there will not be enough free oxygen in the glass, which will increase the number of layered boron-oxygen triangles and reduce the content of boron-oxygen tetrahedron, resulting in a loose glass network structure and unstable chemical properties; if the content of B2O3 is too high, the volatility will also increase, which will also cause the glass composition to be uneven and the chemical stability to be poor.

[0049] As an example, the mass percentage of B2O3may be 10%, 11%, 12%, 15%, 14%, 15%, 16%, 17%, 18%, or any value within the range between any two of the above-mentioned point values. Further, the mass percentage of B2O3is 12% to 16%.

[0050] In the borosilicate glass of the present application, SiO2can provide a glass network basic structure, and B2O3can reduce the melting temperature and improve the chemical stability. The combination of SiO2and B2O3in a specific mass percentage can make the glass have a mixed network structure of [BO4] and [SiO4], thereby optimizing the thermal stability and processing performance of the glass.

[0051] Al2O3is an intermediate oxide, which can reduce the crystallization tendency of the glass, improve the chemical stability, thermal stability, mechanical strength, and hardness of the glass. If the content of Al2O3is too high, it is difficult to obtain a glass with long material properties, and it is difficult to form the glass. Since the aluminum-oxygen tetrahedral structure is more stable than the boron-oxygen tetrahedral structure, in the glass structure unit, the aluminum ion will preferentially obtain free oxygen to form an aluminum-oxygen tetrahedral structure, and then the excess free oxygen will be converted into a boron-oxygen tetrahedral structure with the boron-oxygen triangle. However, due to the large volume of the aluminum-oxygen tetrahedral structure, it is not conducive to reducing the dielectric loss of the glass. Since the Al-O bond is stronger than the Si-O bond, and the [AlO4] tetrahedral structure exists in the network, it plays a role in repairing the network, making the glass network more complete and reducing the thermal expansion coefficient. When the content of Al2O3is low, the aluminum-oxygen tetrahedral network structure formed is insufficient, which can cause the glass to separate into a silicon-rich phase and a boron-rich phase.

[0052] As an example, the mass percentage of Al2O3may be 4%, 5%, 6%, 7%, 8%, or any value within the range between any two of the above-mentioned point values. Further, the mass percentage of Al2O3is 5% to 7%.

[0053] MgO is an extra-network oxide, which can help to reduce the melting point of the glass, reduce the viscosity of the glass at high temperature, promote the melting and fining of the glass, improve the uniformity, increase the hydrolysis resistance, and make the glass more stable, improve the durability of the glass, prevent the glass from crystallizing, and inhibit the movement of alkali metal ions in the glass. MgO can enhance the stability of the glass network space at low temperature, and to some extent, can reduce the thermal expansion coefficient of the glass. However, too much content of MgO can cause the glass network to break and the dielectric performance to deteriorate.

[0054] As an example, the mass percentage of MgO may be 1%, 2%, 3%, 4%, 5%, or any value within the range between any two of the above-mentioned point values. Further, the mass percentage of MgO is 2% to 4%.

[0055] CaO can make the network formed by silicon oxygen tetrahedron [SiO4] relaxed and broken, improve the melting property of glass at high temperature or make the glass not easy to devitrify, can promote the clarification and homogenization of glass liquid by reducing the viscosity of glass liquid, and play a role of fluxing; but too much content will lead to glass network fracture, affect its weather resistance and poor dielectric properties.

[0056] As an example, the mass percentage of CaO can be 4%, 5%, 6%, 7%, 8%, 9%, or any value within the range formed by any two of the above point values. Further, the mass percentage of CaO is 5% to 8%.

[0057] It can be understood that there is a difference in ionic radius between CaO and MgO, and the two can produce a gradient network expansion effect, so that the thermal expansion coefficient of the glass is stable at 45x10 -7 / ℃~60x10 -7 / ℃, realizing precise control of the thermal expansion coefficient and matching with silicon chips.

[0058] In some embodiments, the ratio of the mass percentage of MgO to the mass percentage of CaO is 0.3 to 0.6.

[0059] P2O5 is an important component of the network structure of glass material. When the content of Al2O3 is low, a certain amount of P2O5 can enter the glass network, P 5+ ions form [PO4] tetrahedron in melting, which is connected with [SiO4] network through P-O-Si bond, increases the proportion of bridge oxygen (O_b / O_t value), reduces the ultraviolet absorption group (such as Si-O - ) caused by non-bridge oxygen, makes the ultraviolet cutoff wavelength blue shift to below 190nm, and the transmittance is significantly improved; and P2O5 and SiO2 can react to generate silicon phosphate above 1400℃, increasing the proportion of bridge oxygen to more than 82%. If the content of P2O5 is too low, it cannot generate enough bridge oxygen, so it cannot reduce the dielectric constant and dielectric loss, and the transmittance under ultraviolet light cannot be significantly improved; if P2O5 is added too much, the thermal expansion coefficient will increase significantly, the melting temperature of the glass will increase, and the glass is also prone to devitrification and phase separation.

[0060] As an example, the mass percentage of P2O5 can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, or any value within the range formed by any two of the above point values. Further, the mass percentage of P2O5 is 0.8% to 1.5%.

[0061] ZnO belongs to divalent metal oxide, which has the same effect as alkaline earth metal oxide; in silicate glass system, adding appropriate amount of ZnO can effectively reduce the melting temperature of glass, reduce the transition temperature Tg of glass, and ZnO can react with P2O5 to form Zn 2+ , Zn 2+ can block the migration channel of Na⁺, reduce dielectric loss.

[0062] As an example, the mass percentage of ZnO can be 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, or any value within the range formed by any two of the above point values. Further, the mass percentage of ZnO is 0.5% to 1%.

[0063] In some embodiments, the ratio of the mass percentage of P2O5 to the mass percentage of ZnO is 1 to 2. Further optionally, it is 1.8 to 2. More further optionally, it is 1.8.

[0064] P2O5 and ZnO can act as a deep ultraviolet transmission enhancer, so that the transmittance of the glass in the 190nm deep ultraviolet band reaches 75%, meeting the requirements of EUV lithography for alignment accuracy.

[0065] Ta2O5 can act as a surfactant, through phase separation induction, Ta 5+ combined with [BO3] triangle can form a tantalum-rich phase (Ta-O-B bond), which occurs spinodal phase separation in heat treatment, forming a tantalum and boron-rich region with a size of 20nm to 50nm. The dissolution rate of the tantalum-rich phase in HF is about 8 times faster than that of SiO2 matrix, and vertical nanopores can be produced after etching, increasing the specific surface area. The refractive index of Ta2O5 is quite different from that of the matrix glass, but nanoscale dispersion can make the light scattering rate <1% (λ=190nm), so that the ultraviolet transmittance is >75%. If the content of Ta2O5 is too low, the phase separation is insufficient, and the concentration of Ta 5+ ions is not enough to form a continuous tantalum-rich phase, resulting in a decrease in surface roughness after etching, low bonding strength, lack of nanopore structure, Si-OH density ≤5 / nm², and Cu bonding strength ≤12MPa. If the content of Ta2O5 is too high, barium tantalate (BaTa2O6) and other crystal phases will be precipitated, the size of the ultraviolet scattering precipitated phase will be too large, Rayleigh scattering will be induced, and the 190nm transmittance will drop sharply to <65%; at the same time, the glass will be embrittled, stress will be concentrated at the grain boundary, and the fracture toughness will increase.

[0066] As an example, the mass percentage of Ta2O5 can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, or any value within the range formed by any two of the above points. Further, the mass percentage of Ta2O5 is 0.6% to 1%.

[0067] Sc2O3 is used as a surfactant, in which Sc 3+ Able to replace B in [BO4] 3+ This causes lattice distortion, lowering the phase separation temperature from 850℃ to 750℃, preventing high-temperature crystallization and ensuring glass homogeneity. Meanwhile, Sc... 3+ With F - Able to form stable complexes (ScF6) 3- This accelerates the dissolution of the tantalum-rich phase, forming nanocavities with rough pore walls; furthermore, because the bond energy of Sc-O is greater than that of Na-O, it can block Na... + The migration channel is improved, and dielectric loss is reduced by 40%. If the Sc2O3 content is too low, it will lead to a high phase separation temperature; a lack of Sc... 3+ Lowering the phase separation barrier requires a phase separation temperature greater than 800℃; however, this may lead to uneven etching, slow dissolution rate of the tantalum-rich phase, large fluctuations in pore depth, and weak chemical bonding; simultaneously, due to the lack of Sc-O-Cu bridging bonds, the bonding ratio will be less than 10%, resulting in reduced bonding strength. Excessive Sc2O3 content can cause glass devitrification. 3+ ScBO3 microcrystals are formed with [BO3], and excess Sc 3+ It introduces ion conduction channels, leading to an increase in dielectric loss; and the high expansion coefficient of Sc2O3 will disrupt the CTE uniformity of borosilicate glass, causing the overall CTE value of the glass to increase.

[0068] As an example, the mass percentage of Sc2O3 can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or any value within the range of any two of the above points. Further, the mass percentage of Sc2O3 is 0.2% to 0.6%.

[0069] It is understandable that Ta2O5 and Sc2O3 can form localized enrichment zones during the melting process, which are preferentially dissolved in subsequent acid treatment, producing nanoscale micropores. This can significantly increase the specific surface area of ​​the glass and expose a high density of Si-OH groups, providing ideal bonding sites for metals.

[0070] In some embodiments, the mass percentage ratio of Ta2O5 to Sc2O3 is 1 to 3. Further alternatively, it is 1 to 2; even more preferably, it is 1.17.

[0071] In some embodiments, the borosilicate glass comprises, in mass percent, SiO265% to 70%, B2O312% to 16%, Al2O35% to 7%, MgO 2% to 4%, CaO 5% to 8%, P2O50.8% to 1.5%, ZnO 0.5% to 1%, Ta2O50.6% to 1%, and Sc2O30.2% to 0.6%.

[0072] In some specific examples, the borosilicate glass comprises, in mass percent, SiO266.2%, B2O315.5%, Al2O35.8%, MgO 2.1%, CaO 7.2%, P2O51.2%, ZnO 0.8%, Ta2O50.9%, and Sc2O30.3%.

[0073] In some embodiments, the borosilicate glass further comprises, in mass percent, 0.05% to 0.2% of a fining agent.

[0074] It can be understood that the fining agent in the above content is not affected by the melting or forming atmosphere during the melting process, and does not affect the service life of the kiln.

[0075] For example, the mass percent of the fining agent can be 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.15%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.2%, or any value within the range formed by any two of the above values.

[0076] In some embodiments, the fining agent comprises one or more of NaCl and CeO2.

[0077] In some embodiments, the borosilicate glass has a coefficient of thermal expansion ≤ 55 x 10 -7 / ℃.

[0078] Further, the borosilicate glass has a coefficient of thermal expansion of 45 x 10 -7 / ℃ to 55 x 10 -7 / ℃.

[0079] In some embodiments, the borosilicate glass has a dielectric constant ≤ 5 at 10 GHz.

[0080] Further, the borosilicate glass has a dielectric constant of 4 to 5 at 10 GHz.

[0081] In some embodiments, the borosilicate glass has a dielectric loss ≤ 8.1 x 10-3 .

[0082] Further, the dielectric loss of the borosilicate glass is 6.4x10 -3 8.1x10 -3 .

[0083] The borosilicate glass of the present application has excellent thermal properties, surface properties, dielectric properties, processing properties and optical properties, can be well matched with silicon chips, and can meet the requirements of EUV lithography for alignment accuracy.

[0084] Some embodiments of the present application further provide a preparation method of the borosilicate glass, comprising the following steps:

[0085] S10, providing raw materials for preparation according to the components of the borosilicate glass as described above, and preparing a mixture;

[0086] S20, sequentially performing melting and forming and quenching treatment on the mixture to prepare the borosilicate glass.

[0087] In some embodiments, the step of preparing the mixture in S10 comprises:

[0088] S11, providing raw materials according to the mass percentages of SiO2, B2O3, Al2O3, MgO, CaO, Ta2O5 and Sc2O3, mixing uniformly to prepare a mixed intermediate material;

[0089] S12, mixing the mixed intermediate material, P2O5 powder and ZnO powder at 1300°C-1500°C to prepare the mixture.

[0090] In some embodiments, the mixing of the mixed intermediate material, P2O5 powder and ZnO powder in S12 further comprises the step of introducing a weak oxidizing atmosphere.

[0091] Optionally, the weak oxidizing atmosphere comprises O2 and N2; and further optionally, the volume ratio of O2 and N2 is 1:9. It can be understood that the introduction of the weak oxidizing atmosphere can effectively inhibit the reduction of P 5+ to P 3+ to ensure the density of bridging oxygen.

[0092] Since P2O5 is prone to volatilize under high temperature conditions, the content of phosphorus fluctuates; at the same time, excessive ZnO can cause the precipitation of zinc aluminate, increasing light scattering, therefore, the present application adopts the method of gradient feeding to reduce the fluctuation of the content of phosphorus and the precipitation of zinc aluminate.

[0093] As an example, the temperature of the mixing in S12 can be 1300℃, 1310℃, 1320℃, 1330℃, 1340℃, 1350℃, 1360℃, 1370℃, 1380℃, 1390℃, 1400℃, 1410℃, 1420℃, 1430℃, 1440℃, 1450℃, 1460℃, 1470℃, 1480℃, 1490℃, 1500℃, or any value within a range defined by any two of the above values.

[0094] In some embodiments, the temperature of the melt forming in S20 is 1550℃ to 1650℃, and the time is 4h to 8h.

[0095] As an example, the temperature of the melt forming can be 1550℃, 1560℃, 1570℃, 1580℃, 1590℃, 1600℃, 1600℃, 1610℃, 1620℃, 1630℃, 1640℃, 1650℃, or any value within a range defined by any two of the above values. The temperature of the melt forming can be 4h, 5h, 6h, 7h, 8h, or any value within a range defined by any two of the above values.

[0096] In some embodiments, the method of melt forming includes one or more of float forming, slot down-draw forming, and overflow forming.

[0097] In some embodiments, the quenching process includes a first quenching process and a second quenching process performed in sequence, the cooling speed of the first quenching process is 40℃ / s to 60℃ / s, and the cooling speed of the second quenching process is 0.5℃ / s to 2℃ / s.

[0098] It should be noted that when the cooling temperature is lowered to Tg+50℃ of the glass through the first quenching process, the cooling speed of the second quenching process is continued to slow down. Through the double-stage quenching process, the internal stress can be effectively eliminated and the Ta / Sc oxide phase separation can be promoted.

[0099] As an example, the cooling speed of the first quenching process can be 40℃ / s, 41℃ / s, 42℃ / s, 43℃ / s, 44℃ / s, 45℃ / s, 46℃ / s, 47℃ / s, 48℃ / s, 49℃ / s, 50℃ / s, 51℃ / s, 52℃ / s, 53℃ / s, 54℃ / s, 55℃ / s, 56℃ / s, 57℃ / s, 58℃ / s, 59℃ / s, 60℃ / s, or any value within a range defined by any two of the above values. Further, it can be 45℃ / s to 55℃ / s.

[0100] For example, the cooling rate of the second quenching treatment can be 0.5°C / s, 0.6°C / s, 0.7°C / s, 0.8°C / s, 0.9°C / s, 1°C / s, 1.1°C / s, 1.2°C / s, 1.3°C / s, 1.4°C / s, 1.5°C / s, 1.6°C / s, 1.7°C / s, 1.8°C / s, 1.9°C / s, 2°C / s, or any value within a range defined by any two of the above values.

[0101] In some embodiments, after the quenching treatment, the method further comprises a step of etching the mixture.

[0102] In some embodiments, the etching treatment comprises an acid etching treatment and an alkaline activation treatment performed in sequence.

[0103] In some optional examples, the solution of the acid etching treatment comprises a hydrofluoric acid solution and a sulfuric acid solution.

[0104] Further, in the solution of the acid etching treatment, the volume ratio of the hydrofluoric acid solution is 5%, and the volume ratio of the sulfuric acid solution is 15%. It can be understood that the acid etching treatment with the acid solution can selectively dissolve the Ta / Sc-rich phase to form nanoscale pits.

[0105] In some optional examples, the solution of the alkaline activation treatment comprises a sodium hydroxide solution and a cetyltrimethylammonium bromide solution.

[0106] Further, in the solution of the alkaline activation treatment, the concentration of the sodium hydroxide solution is 1 mol / L, and the concentration of the cetyltrimethylammonium bromide solution is 0.1 mol / L. It can be understood that the activation treatment with the alkaline solution can expand the surface pores and expose more Si-OH groups, so that the surface silicon hydroxyl density is increased by more than 2.3 times that of conventional glass.

[0107] Some embodiments of the present application also provide a glass product comprising the borosilicate glass described above or the borosilicate glass prepared by the method described above.

[0108] For example, the glass product described above comprises a glass substrate.

[0109] The present application will be further described in conjunction with specific examples and comparative examples, but should not be construed as limiting the scope of protection of the present application. The raw materials involved in the following specific examples, if not specifically stated, can be sourced from the market, and the instruments used, if not specifically stated, can be sourced from the market. The processes involved, if not specifically stated, are routinely selected by those skilled in the art.

[0110] Example 1

[0111] (1) Provide raw materials for preparation according to the percentages of SiO2, B2O3, Al2O3, MgO, CaO, Ta2O5, Sc2O3 in the borosilicate glass described in Table 1, mix the raw materials by stirring, place the mixed materials in a platinum crucible greater than 600 mL, place the platinum crucible in a silicon molybdenum furnace, prepare the mixed intermediate material; mix the mixed intermediate material with P2O5-ZnO mixed powder by heating to 1400℃, pass in a weak oxidizing atmosphere (O2:N2=1:9), heat to 1600℃ and melt and clarify for 4h, homogenize and cast into a mold to form. After melting, use double-stage quenching: the first stage is rapid cooling at 50℃ / s to a temperature 50℃ above the vitrification cooling temperature (Tg), and the second stage is slow cooling at 1℃ / s to room temperature to prepare the borosilicate glass.

[0112] (2) Test the properties of the borosilicate glass prepared in step (1): refer to GB / T16920-2015 and test using a German Zwick PC402L horizontal dilatometer to obtain the thermal expansion coefficient CTE (50℃~300℃) and the transition temperature Tg. Refer to the test method in GJB 1651A-201X, process the glass to be tested into a rectangular sheet-shaped sample of 22.86mm x 10.16mm x 1mm, use a PNA-N5234A type vector network analyzer, and measure the dielectric constant and dielectric loss of the borosilicate glass at a frequency of 10GHz using the waveguide method. The performance test results are shown in Table 2.

[0113] (3) Further gradient etching treatment is performed on the borosilicate glass prepared in step (1), which specifically includes the following steps:

[0114] First step of acidic etching treatment: use a mixed acid solution of HF (5%) / H2SO4 (15%) at a volume percentage of 40℃ for 5min.

[0115] First step of alkaline activation treatment: use a mixed solution of NaOH (1M) / CTAB (0.1M) at 60℃ for 5min.

[0116] (4) Test the Si-OH density and Cu bonding strength of the borosilicate glass after gradient etching treatment.

[0117] Si-OH density testing includes XPS testing and deuteration exchange-infrared spectroscopy; wherein the XPS testing is performed according to ISO 14701:2011, the Si-OH group proportion is calculated by analyzing the O1s spectral peak (characteristic peak at binding energy 532.5 eV) deconvolution. Formula: Si-OH density = A Si-OH / A total x surface Si atomic density; wherein A Si-OHA Si-OH peak area, A total A total oxygen peak area. Deuterium exchange-infrared spectroscopy was performed according to ASTM E2108-16, the glass sample to be tested was exposed to D2O vapor, and the characteristic peak intensity of Si-OD at 2880 cm -1 was monitored, and the Si-OH density was converted by the peak area. The sample size was 10x10 mm 2 , and the surface roughness Ra was ≤0.5 nm.

[0118] Cu bonding strength test: according to the cross tensile method described in ASTM D3167, the glass substrate with deposited Cu film was bonded with another Cu plated substrate using epoxy adhesive, and was vertically stretched to the glass, and the maximum tensile force F max / A was recorded. The actual contact area of the bonding interface was accurately measured by a microscope or laser scanning to avoid errors caused by micropores or edge defects; and the Cu bonding strength was calculated according to σ=KxF max / A; wherein σ represents the bonding strength (unit: MPa, i.e. N / mm 2 ), F max represents the maximum tensile force (N) when the sample fails, A represents the effective area of the bonding interface; and K represents the correction coefficient in the glass sample of the present application.

[0119] (5) Ultraviolet transmittance test

[0120] The ultraviolet-visible spectrophotometry was used, and the standardization process for testing the transmittance of materials by integrating sphere method was specified in ASTM E903-20, covering the wavelength range of 190 nm to 2500 nm. The sample surface was required to be flat and optically uniform. The test procedure was as follows: the light source emitted 190 nm deep ultraviolet light, which was spectrally dispersed by a monochromator; the light beam was converted into isotropic circularly polarized light by a depolarizer to avoid polarization errors; a 35 mm x 35 mm sample was placed in the light path, and a detector measured the incident light intensity (I0) and the transmitted light intensity (I); and the transmittance calculation formula was T=I / I0x100%.

[0121] The results of Si-OH density test, Cu bonding strength test and ultraviolet transmittance test are shown in Table 2.

[0122] Examples 2-22 are basically the same as Example 1, except that the components of the borosilicate glass in step (1) are different, and different amounts of raw materials are provided accordingly; specifically, the component proportions of Examples 2-22 are shown in Table 1; and the performance test results of Examples 2-22 are shown in Table 2.

[0123] Example 23 is substantially identical to Example 9, except that the preparation method is different, specifically, in Example 23, step (1) is to add all the raw materials for forming the SiO2, B2O3, Al2O3, MgO, CaO, Ta2O5, Sc2O3, P2O5 and ZnO components into a platinum crucible, melt and clarify at 1600°C for 4h, homogenize and cast into a mold to form. After melting, a two-stage quenching is used: the first stage is to rapidly cool at 50°C / s to a temperature 50°C above the glass transition temperature (Tg), and the second stage is to slowly cool at 1°C / s to room temperature, to prepare the borosilicate glass.

[0124] Table 1

[0125]

[0126] Table 2

[0127]

[0128] In Example 23, P2O5 and ZnO are not added in a gradient manner; the volatilization rate of P2O5 during preparation is more than 20%, which reduces the bridging oxygen proportion in the glass structure and the 190nm transmittance, and precipitates ZnAl2O4 crystal phase, and also slightly increases the dielectric loss.

[0129] Comparative Examples 1-5 are substantially identical to Example 9, except that the mass of some components of the borosilicate glass is different; the glass components of Comparative Examples 1-5 are shown in Table 3, and the performance test results are shown in Table 4.

[0130] Table 3

[0131]

[0132] Table 4

[0133]

[0134] In Comparative Example 1, Ta2O5 is not added, the tantalum-rich phase in the glass structure is separated, and no nanopores are formed in the glass structure after acid etching treatment, which causes the Si-OH density to drop sharply and the Cu bonding strength to decrease, indicating that Ta2O5 can induce the formation of nanopore structure and plays an important role in surface activation.

[0135] In Comparative Example 2, Sc2O3 is not added, the phase separation temperature of the glass structure increases, which causes the glass phase separation to be uneven, the etching hole depth to fluctuate greatly, the Cu bonding strength to decrease, and the dielectric loss to increase. This indicates that Sc2O3 can effectively reduce the phase separation temperature and improve the etching uniformity.

[0136] The mass percentage of B2O3 in Comparative Example 3 is only 8%, and the prepared glass network structure is loose, so that the thermal expansion coefficient increases, the chemical stability decreases, and the dielectric loss increases, indicating that B2O3 has a significant effect on network stability and CTE regulation.

[0137] The mass percentage of CaO in Comparative Example 4 reaches 10%, so that the glass network structure is destroyed, the thermal expansion coefficient increases, the thermal distortion temperature rises, and the dielectric constant and dielectric loss increase, indicating that excessive CaO has a negative impact on thermal matching.

[0138] The mass percentage of MgO in Comparative Example 5 reaches 6%, and Mg 2+ Aggregation causes microphase separation, resulting in increased glass brittleness, precipitation of MgSiO3 crystal phase, and further increased 190nm scattering, reduced transmittance, and increased thermal expansion coefficient, indicating that limiting the content of MgO within a specific range of the present application can protect against crystallization and optical performance.

[0139] The technical features of the above-described embodiments can be combined arbitrarily, and to make the description concise, not all possible combinations of the technical features in the above-described embodiments are described, however, as long as the combinations of the technical features do not exist contradictory, they should be considered as the scope of the present disclosure.

[0140] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent. It should be noted that for those skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are all within the scope of the present application. Therefore, the scope of the present application should be subject to the appended claims.

Claims

1. A borosilicate glass characterized in that, comprises, by mass percentage, SiO2 60%~75%, B2O3 10%~18%, Al2O3 4%~8%, MgO 1%~5%, CaO 4%~9%, P2O5 0.5%~2%, ZnO 0.2%~2%, Ta2O5 0.3%~1.5%, and Sc2O3 0.1%~1%.

2. The borosilicate glass of claim 1, wherein comprises, by mass percentage, SiO2 65%~70%, B2O3 12%~16%, Al2O3 5%~7%, MgO 2%~4%, CaO 5%~8%, P2O5 0.8%~1.5%, ZnO 0.5%~1%, Ta2O5 0.6%~1%, and Sc2O3 0.2%~0.6%.

3. The borosilicate glass of any one of claims 1-2, wherein, The components of the borosilicate glass further comprise, by mass percentage, 0.05%~0.2% of a fining agent; Optionally, the fining agent comprises one or more of NaCl and CeO2.

4. The borosilicate glass according to any one of claims 1 to 2, wherein, The borosilicate glass satisfies at least one of the following characteristics: (1) the borosilicate glass has a coefficient of thermal expansion < 55 x 10 -7 / °C; (2) The borosilicate glass has a dielectric constant ≤5 at 10 GHz; (3) the dielectric loss of the borosilicate glass is ≤ 8.1 x 10 -3 at 10 GHz 5. A method of making a borosilicate glass, characterized in that, comprises the following steps: The components of the borosilicate glass according to any one of claims 1~4 provide raw materials for preparation, and a mixture is prepared; The mixture is sequentially subjected to melting forming and quenching treatment to prepare the borosilicate glass.

6. The method of making borosilicate glass according to claim 5, wherein, The step of preparing a mixture comprises: Raw materials are provided in mass percentages of SiO2, B2O3, Al2O3, MgO, CaO, Ta2O5, and Sc2O3, and are uniformly mixed to prepare a mixed intermediate material; The mixed intermediate material, P2O5 powder, and ZnO powder are mixed at 1300°C~1500°C to prepare a mixture.

7. The method of making borosilicate glass according to claim 5 or 6, wherein The method for preparing the borosilicate glass satisfies at least one of the following characteristics: (1) The temperature of the melting forming is 1550°C~1650°C, and the time is 4h~8h; (2) The quenching treatment comprises sequentially performed first quenching treatment and second quenching treatment, the cooling speed of the first quenching treatment is 40°C / s~60°C / s, and the cooling speed of the second quenching treatment is 0.5°C / s~2°C / s; (3) The method for melting forming comprises one or more of float forming, slot down-draw forming, and overflow forming.

8. The method of making a borosilicate glass according to claim 5 or 6, wherein, After the quenching treatment, a step of etching treatment is further included; Optionally, the etching treatment comprises sequentially performed acidic etching treatment and alkaline activation treatment; Further optionally, the solution of the acidic etching treatment comprises hydrofluoric acid solution and sulfuric acid solution; Further optionally, the solution of the alkaline activation treatment comprises sodium hydroxide solution and cetyltrimethylammonium bromide solution.

9. A glass article, characterized by, The borosilicate glass prepared by the method for preparing the borosilicate glass according to any one of claims 1~4 or 5~8.

10. The application of borosilicate glass as described in any one of claims 1 to 4 or borosilicate glass prepared by the method described in any one of claims 5 to 8 in the preparation of integrated antennas, electronic packaging or microelectromechanical system packaging.

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