阅读说明：本技术 低介电常数玻璃 (Low dielectric constant glass ) 是由 蔡冬雪 于 2021-01-12 设计创作，主要内容包括：本发明提供一种低介电常数玻璃,所述玻璃的组分以重量百分比表示,含有：SiO-2：55～80％、B-2O-3：10～40％、Al-2O-3：1～10％、Rn-2O：0.5～10％,其中SiO-2/B-2O-3为1.5～3.5,所述Rn-2O为Li-2O、Na-2O、K-2O中的一种以上。通过合理的组分设计,本发明玻璃的量产工艺性能好,相对介电常数较低,为电子领域的介电材料选择带来了更大的自由度。(The invention provides a low dielectric constant glass, which comprises the following components in percentage by weight: SiO 2 2 ：55～80％、B 2 O 3 ：10～40％、Al 2 O 3 ：1～10％、Rn 2 O: 0.5 to 10% of SiO 2 /B 2 O 3 1.5 to 3.5, the Rn 2 O is Li 2 O、Na 2 O、K 2 And O or more. Through reasonable component design, the glass has good mass production process performance and lower relative dielectric constant, and brings greater freedom for the selection of dielectric materials in the electronic field.)

1. Low dielectric constant glass, characterized in that its composition, expressed in weight percent, comprises: SiO 2₂：55～80％、B₂O₃：10～40％、Al₂O₃：1～10％、Rn₂O: 0.5 to 10% of SiO₂/B₂O₃1.5 to 3.5, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

2. The low dielectric constant glass according to claim 1, further comprising, in weight percent: and (3) RO: 0-5% of a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

3. Low dielectric constant glass, characterized in that its composition, expressed in weight percentage, is represented by SiO₂：55～80％、B₂O₃：10～40％、Al₂O₃：1～10％、Rn₂O: 0.5-10%, RO: 0-5% of a clarifying agent: 0 to 1% of SiO₂/B₂O₃1.5 to 3.5, the Rn₂O is Li₂O、Na₂O、K₂More than one of O, RO is more than one of BaO, SrO, CaO and MgO, and the clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

4. A low dielectric constant glass according to any of claims 1 to 3, having a composition expressed in weight percent, wherein: SiO 2₂/B₂O₃2.0 to 3.2, preferably SiO₂/B₂O₃2.0 to 3.0, more preferably SiO₂/B₂O₃2.5 to 3.0.

5. A low dielectric constant glass according to any of claims 1 to 3, having a composition expressed in weight percent, wherein: al (Al)₂O₃/B₂O₃0.05 to 0.4, preferably Al₂O₃/B₂O₃0.05 to 0.3, more preferably Al₂O₃/B₂O₃0.05 to 0.2, and more preferably Al₂O₃/B₂O₃0.08 to 0.15.

6. A low dielectric constant glass according to any of claims 1 to 3, having a composition expressed in weight percent, wherein: rn₂O/(SiO₂+B₂O₃) 0.01 to 0.1, preferably Rn₂O/(SiO₂+B₂O₃) 0.01 to 0.08, more preferably Rn₂O/(SiO₂+B₂O₃) 0.01 to 0.05.

7. A low dielectric constant glass according to any of claims 1 to 3, having a composition expressed in weight percent, wherein: RO/Rn₂O is 0.1 to 1.0, preferably RO/Rn₂O is 0.2 to 0.8, and RO/Rn is more preferable₂O is 0.3 to 0.7.

8. A low dielectric constant glass according to any of claims 1 to 3, having a composition expressed in weight percent, wherein: SiO 2₂: 58 to 75%, preferably SiO₂: 60-75%; and/or B₂O₃: 12 to 35%, preferably B₂O₃: 15-30%; and/or Al₂O₃: 1 to 8%, preferably Al₂O₃: 1-5%; and/or Rn₂O: 1 to 8%, preferably Rn₂O: 2-5%; and/or RO: 0.5-4%, preferably RO: 1-3%; and/or a clarifying agent: 0-0.8%, preferably clarifying agent: 0 to 0.5 percent.

9. The low dielectric constant glass according to any one of claims 1 to 3, wherein the low dielectric constant glass has a relative dielectric constant ε of 5.5 or less, preferably 5.0 or less, and/or a volume resistivity ρ of 4.0X 10¹³Omega cm or more, preferably 5.0X 10¹³Omega cm or more.

10. The low dielectric constant glass of any one of claims 1 to 3, wherein the low dielectric constant glass has a water resistance stability D_wIs 2 or more, preferably 1, and/or a thermal expansion coefficient alpha_-30～120℃Is 4.5 multiplied by 10^-6/. degree.C.or less, preferably 4.0X 10^-6Below/° c.

Technical Field

The invention relates to glass, in particular to low dielectric constant glass.

Background

In recent years, the degree of integration of integrated circuits has been gradually increased, and the operating frequency ranges of radio frequency connectors, microwave devices, and the like have been greatly increased. In order to reduce the impedance delay and power loss caused by the impedance delay and power loss, it is important to reduce the parasitic capacitance of the dielectric layer in addition to using low-resistivity metal. The capacitance (C) is proportional to the dielectric constant, and therefore, by using a low dielectric constant material as an interconnection medium, the impedance delay can be reduced, thereby satisfying the demand for the development of integrated circuits. In addition, the research on low dielectric constant materials in the semiconductor field is increasing, and the dielectric properties of glass have become one of the important criteria for determining the application of glass in the electronic field. Therefore, the development of glass materials with low dielectric constants is a new issue for researchers in the development of the times.

In the glass materials in the prior art, the relative dielectric constant of the low dielectric constant glass is generally greater than 5.5, and if a glass material with a relative dielectric constant lower than 5.5, even lower than 5.0 can be developed, the application range of the glass material in the electronic field can be better widened, and the performance of the electronic material in the electrical aspect can be effectively enhanced. However, if the above glass is required to have a relative dielectric constant of less than 5.0, it is required to be different from conventional glass in composition design, and it is generally difficult to melt, clarify, and have poor intrinsic quality. If the high-temperature viscosity of the glass is high, the production difficulty of the glass blank is increased firstly, and then bubbles in the glass liquid are difficult to remove, so that the inherent quality of the glass is poor, and the yield is reduced.

Disclosure of Invention

The invention aims to solve the technical problem of providing glass with good mass production process performance and low relative dielectric constant.

The technical scheme adopted by the invention for solving the technical problem is as follows:

(1) the low dielectric constant glass comprises the following components in percentage by weight: SiO 2₂：55～80％、B₂O₃：10～40％、Al₂O₃：1～10％、Rn₂O: 0.5 to 10% of SiO₂/B₂O₃1.5 to 3.5, the Rn₂O is Li₂O、Na₂O、K₂And O or more.

(2) The low dielectric constant glass according to (1), which comprises the following components in percentage by weight: and (3) RO: 0-5% of a clarifying agent: 0-1%, RO is more than one of BaO, SrO, CaO and MgO, and a clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(3) Low dielectric constant glass having a composition expressed in weight percent of SiO₂：55～80％、B₂O₃：10～40％、Al₂O₃：1～10％、Rn₂O: 0.5-10%, RO: 0-5% of a clarifying agent: 0 to 1% of SiO₂/B₂O₃1.5 to 3.5, the Rn₂O is Li₂O、Na₂O、K₂More than one of O, RO is one of BaO, SrO, CaO and MgOThe clarifying agent is Sb₂O₃、SnO₂、SnO、CeO₂One or more of (a).

(4) The low dielectric constant glass according to any one of (1) to (3), wherein the glass comprises, in weight percent: SiO 2₂/B₂O₃2.0 to 3.2, preferably SiO₂/B₂O₃2.0 to 3.0, more preferably SiO₂/B₂O₃2.5 to 3.0.

(5) The low dielectric constant glass according to any one of (1) to (3), wherein the glass comprises, in weight percent: al (Al)₂O₃/B₂O₃0.05 to 0.4, preferably Al₂O₃/B₂O₃0.05 to 0.3, more preferably Al₂O₃/B₂O₃0.05 to 0.2, and more preferably Al₂O₃/B₂O₃0.08 to 0.15.

(6) The low dielectric constant glass according to any one of (1) to (3), wherein the glass comprises, in weight percent: rn₂O/(SiO₂+B₂O₃) 0.01 to 0.1, preferably Rn₂O/(SiO₂+B₂O₃) 0.01 to 0.08, more preferably Rn₂O/(SiO₂+B₂O₃) 0.01 to 0.05.

(7) The low dielectric constant glass according to any one of (1) to (3), wherein the glass comprises, in weight percent: RO/Rn₂O is 0.1 to 1.0, preferably RO/Rn₂O is 0.2 to 0.8, and RO/Rn is more preferable₂O is 0.3 to 0.7.

(8) The low dielectric constant glass according to any one of (1) to (3), wherein the glass comprises, in weight percent: SiO 2₂: 58 to 75%, preferably SiO₂: 60-75%; and/or B₂O₃: 12 to 35%, preferably B₂O₃: 15-30%; and/or Al₂O₃: 1 to 8%, preferably Al₂O₃: 1-5%; and/or Rn₂O: 1 to 8%, preferably Rn₂O: 2-5%; and/or RO: 0.5-4%, preferably RO: 1-3%; and/or clarificationPreparation: 0-0.8%, preferably clarifying agent: 0 to 0.5 percent.

(9) The low dielectric constant glass according to any one of (1) to (3), wherein the low dielectric constant glass has a relative dielectric constant ε of 5.5 or less, preferably 5.0 or less, and/or a volume resistivity ρ of 4.0 × 10¹³Omega cm or more, preferably 5.0X 10¹³Omega cm or more.

(10) The low dielectric constant glass according to any one of (1) to (3), which has a stability to water action D_wIs 2 or more, preferably 1, and/or a thermal expansion coefficient alpha_-30～120℃Is 4.5 multiplied by 10^-6/. degree.C.or less, preferably 4.0X 10^-6Below/° c.

The invention has the beneficial effects that: through reasonable component design, the glass has good mass production process performance and lower relative dielectric constant, and brings greater freedom for the selection of dielectric materials in the electronic field.

In some embodiments, the glass obtained by the present invention has a volume resistivity of up to 4.0X 10¹³Omega cm or more, and has better insulation effect.

In some embodiments, the glass obtained by the present invention has a low coefficient of thermal expansion, which can be matched to quartz silicon and the like.

In some embodiments, the glasses obtained by the present invention have excellent chemical stability and do not significantly degrade long-term use.

Detailed Description

The embodiments of the low dielectric constant glass of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the object of the present invention. Although the description of the overlapping portions may be omitted as appropriate, the invention is not limited thereto, and the low dielectric constant glass of the present invention may be simply referred to as glass in the following description.

[ Low dielectric constant glass ]

The ranges of the respective components (composition components) of the low dielectric constant glass of the present invention are explained below. In the present specification, the contents and total contents of the respective components are all expressed in terms of weight percent (wt%) relative to the total amount of glass matter converted into the composition of oxides, if not specifically stated. Here, the term "composition converted to oxides" means that when oxides, complex salts, hydroxides, and the like used as raw materials of the low dielectric constant glass composition component of the present invention are decomposed in the melt and converted to oxides, the total amount of the oxides is defined as 100%.

Unless otherwise indicated herein, the numerical ranges set forth herein include upper and lower values, and the terms "above" and "below" include the endpoints, and all integers and fractions within the range, and are not limited to the specific values listed in the defined range. As used herein, "and/or" is inclusive, e.g., "A and/or B," and means A alone, B alone, or both A and B.

< essential Components and optional Components >

SiO₂And B₂O₃The glass is a network forming component which forms the glass of the invention, is the basis of forming the glass, and the content of the glass is closely related to key indexes of glass forming stability, relative dielectric constant, volume resistivity, thermal expansion coefficient and the like of the glass. If SiO₂If the content exceeds 80%, the glass becomes difficult to melt and the melting difficulty increases, so that SiO₂The content of (b) is 80% or less, preferably 75% or less; if SiO₂Less than 55%, the chemical stability, especially the stability against water action, of the glass is reduced, so that SiO₂The content of (b) is 55% or more, preferably 58% or more, more preferably 60% or more.

B₂O₃If the content of (B) exceeds 40%, the chemical stability of the glass is lowered and the thermal expansion coefficient is increased, so that B₂O₃The content of (b) is 40% or less, preferably 35% or less, more preferably 30% or less. On the other hand, B₂O₃If the content of (B) is less than 10%, the resistivity of the glass is lowered and the relative dielectric constant is difficult to meet the design requirements, so that B₂O₃The content of (b) is 10% or more, preferably 12% or more, more preferably 15% or more.

The inventor finds that SiO through a great deal of experimental research₂And B₂O₃To a certain extent determines B₂O₃The structural state in the glass further greatly affects the volume resistivity of the glass. Further, when SiO₂Content of (A) and (B)₂O₃Ratio between contents of (A) SiO₂/B₂O₃When the volume resistivity of the glass is more than 3.5, the volume resistivity of the glass is slowly increased, the glass is difficult to melt, the melting difficulty is increased, a large amount of bubbles and stones are easily generated in the glass, and the yield of the glass is reduced, so that the SiO₂/B₂O₃The value of (b) is preferably 3.5 or less, more preferably 3.2 or less, and further preferably 3.0 or less. If SiO₂/B₂O₃Less than 1.5, the volume resistivity of the glass is rapidly reduced and cannot meet the design requirements, so that SiO₂/B₂O₃The value of (b) is preferably 1.5 or more, more preferably 2.0 or more, and further preferably 2.5 or more.

Rn₂O is an alkali metal oxide (Rn)₂O is Li₂O、Na₂O、K₂O) or more), B in the glass of the present system₂O₃Is a layered structure of SiO₂Is a frame-shaped structure, and is difficult to form uniform melt due to different structures, and B is difficult to form during the high-temperature cooling process₂O₃And SiO₂The two glasses are mutually insoluble and are enriched into a system, and phase separation is further generated. When Rn is present in the glass₂O, the structure of boron changes, Rn₂Free oxygen of O makes partial boron oxygen triangle (BO)₃]Conversion to boron-oxygen tetrahedron [ BO₄]The structure of boron is changed from a layer shape to a frame shape and is B₂O₃And SiO₂Forming uniform and consistent glass creating conditions. When the contents of silicon and boron in the glass are constant, Rn₂When the O content exceeds 10%, the glass structure becomes loose and the relative dielectric constant of the glass increases, so that Rn₂The content of O is 10% or less, preferably 8% or less, and more preferably 5% or less. If Rn₂The content of O is less than 0.5 percent,the phase separation of the glass occurs, and the crystallization resistance is sharply reduced. Rn is thus₂The content of O is 0.5% or more, preferably 1% or more, and more preferably 2% or more.

In some embodiments of the invention, when Rn₂O and SiO₂、B₂O₃SiO in total content₂+B₂O₃Ratio Rn of₂O/(SiO₂+B₂O₃) When the dielectric constant is more than 0.1, the structure of the glass is loose, and the relative dielectric constant is difficult to meet the design requirement, so Rn₂O/(SiO₂+B₂O₃) Preferably 0.1 or less, more preferably 0.08 or less, and still more preferably 0.05 or less. If Rn₂O/(SiO₂+B₂O₃) Less than 0.01, phase separation and crystallization of the glass occur, and the chemical stability requirement cannot be met, so Rn₂O/(SiO₂+B₂O₃) Preferably 0.01 or more.

Al₂O₃Rn can be prevented in glass₂O and B₂O₃Aggregation causes phase separation and devitrification of the glass and increases the chemical stability of the glass. When Al is in the glass₂O₃When the content exceeds 10%, the content is determined by [ AlO ]₄]Than [ BO ]₄]Stable, [ BO₄]Tetrahedral body is broken to form [ BO₃]The triangular body makes the glass structure loose, the glass performance is deteriorated, and the relative dielectric constant is rapidly increased, which is contrary to the object of the present invention to lower the relative dielectric constant of the glass. Thus Al₂O₃The content of (b) is 10% or less, preferably 8% or less, more preferably 5% or less. If Al is present₂O₃Less than 1%, the devitrification resistance of the glass is drastically reduced, so that Al is present₂O₃The content of (B) is 1% or more.

In some embodiments of the invention, Al₂O₃And B₂O₃The relative amounts of (B) will to some extent determine B₂O₃The structural state in the glass further has a great influence on the chemical stability of the glass. Further, when Al is present₂O₃And B₂O₃Ratio of (A) to (B) Al₂O₃/B₂O₃If it exceeds 0.4, the chemical stability of the glass is lowered, so Al is preferable₂O₃/B₂O₃Is 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less, and still more preferably 0.15 or less. If Al is present₂O₃/B₂O₃Less than 0.05, the glass is easy to generate phase separation and crystallization and can not meet the requirement of chemical stability, so the Al₂O₃/B₂O₃The value of (b) is preferably 0.05 or more, more preferably 0.08 or more.

RO is an alkaline earth metal oxide (RO is one or more of BaO, SrO, CaO and MgO), and in the present invention, the relative permittivity of the glass can be reduced by containing a small amount of RO, but if the content of RO exceeds 5%, the relative permittivity of the glass increases on the contrary, and therefore the content of RO is 0 to 5%, preferably 0.5 to 4%, more preferably 1 to 3%.

Through a great deal of experimental research of the inventor, RO and Rn are found₂The relative amount of O has a large influence on the thermal expansion coefficient of the glass. Further, if RO and Rn₂Ratio of O RO/Rn₂O is more than 1.0, so that the total amount of ions outside the network is increased, and the thermal expansion coefficient of the glass is increased; if RO/Rn₂O is less than 0.1, the ions outside the network of the glass are mainly alkali metal ions, a small amount of alkaline earth metal ions can not effectively generate a blocking effect, and the thermal expansion coefficient of the glass can not meet the requirement. Thus, RO/Rn₂The value of O is preferably 0.1 to 1.0, more preferably 0.2 to 0.8, and further preferably 0.3 to 0.7.

In some embodiments of the invention, the Sb content is 0-1%₂O₃、SnO₂SnO and CeO₂One or more components of the glass can be used as a clarifying agent to improve the clarifying effect of the glass. However, the invention has a reasonable formula design and a good clarifying effect, so that the invention preferably contains 0-0.8% of clarifying agent, more preferably contains 0-0.5% of clarifying agent, and further preferably does not contain clarifying agent.

< component which should not be contained >

In the glass of the present invention, even when a small amount of oxides of transition metals such as V, Cr, Mn, Fe, Co, Ni, Cu, Ag, and Mo are contained singly or in combination, the glass is colored and absorbs at a specific wavelength in the visible light region, thereby impairing the property of the glass of the present invention to improve the effect of visible light transmittance.

In recent years, oxides of Th, Cd, Tl, Os, Be, and Se tend to Be used as harmful chemical substances in a controlled manner, and measures for protecting the environment are required not only in the glass production process but also in the processing process and disposal after commercialization. Therefore, when importance is attached to the influence on the environment, it is preferable that these components are not substantially contained except for inevitable mixing. Thus, the low dielectric constant glass becomes practically free from substances contaminating the environment. Therefore, the low dielectric constant glass of the present invention can be manufactured, processed, and disposed of without taking special measures for environmental measures.

To achieve environmental friendliness, the low dielectric constant glass of the present invention does not contain As₂O₃And PbO.

"0%" or "0%" is not contained in the present invention, and means that the compound, molecule, element or the like is not intentionally added as a raw material to the low dielectric constant glass of the present invention; however, it is within the scope of the present invention that certain impurities or components, which are not intentionally added, may be present as raw materials and/or equipment for producing the low dielectric constant glass and may be present in small or trace amounts in the final low dielectric constant glass.

Next, the performance of the low dielectric constant glass of the present invention will be described.

< relative dielectric constant >

The relative dielectric constant (. epsilon.) of the glass was measured according to the method specified in CS-158-2018.

In some embodiments, the low dielectric constant glass of the present invention has a relative dielectric constant (. epsilon.) of 5.5 or less, preferably 5.0 or less.

< volume resistivity >

The volume resistivity (. rho.) of the glass was measured according to the method specified in CS-157-.

In some embodiments, the low dielectric constant glass of the present invention has a volume resistivity (ρ) of 4.0 × 10¹³Omega cm or more, preferably 5.0X 10¹³Omega cm or more.

< stability against Water action >

Stability of the glass to Water action (D)_w) (powder method) the test was carried out according to the method prescribed in GB/T17129.

In some embodiments, the low dielectric constant glass of the present invention has stability to water action (D)_w) Is 2 or more, preferably 1.

< coefficient of thermal expansion >

Coefficient of thermal expansion (alpha) of glass_-30～120℃) Testing according to the method specified in GB/T7962.16-2010.

In some embodiments, the low dielectric constant glasses of the present invention have a coefficient of thermal expansion (α)_-30～120℃) Is 4.5 multiplied by 10^-6/. degree.C.or less, preferably 4.0X 10^-6Below/° c.

[ production method ]

The method for manufacturing the low dielectric constant glass comprises the following steps: the glass is produced by adopting conventional raw materials and conventional processes, carbonate, nitrate, sulfate, hydroxide, oxide and the like are used as raw materials, the materials are mixed according to a conventional method, the mixed furnace burden is put into a smelting furnace (such as a platinum crucible, a quartz crucible and the like) at 1580-1630 ℃ for smelting, and after clarification, stirring and homogenization, homogeneous molten glass without bubbles and undissolved substances is obtained, and the molten glass is cast in a mold and annealed. Those skilled in the art can appropriately select the raw materials, the process method and the process parameters according to the actual needs.

< Low dielectric constant glass example >

In order to further clarify the explanation and explanation of the technical solution of the present invention, the following non-limiting examples are provided.

This example was made using the above-mentioned low dielectric constant glassThe production method yielded low dielectric constant glasses having the compositions shown in tables 1 to 2. In addition, the characteristics of each glass were measured by the test method described in the present invention, and the measurement results are shown in tables 1 to 2, wherein SiO is₂/B₂O₃Is denoted by K1; al (Al)₂O₃/B₂O₃Is denoted by K2; rn₂O/(SiO₂+B₂O₃) Is denoted by K3; RO/Rn₂The value of O is denoted by K4.

Table 1.

Table 2.