阅读说明：本技术 一种低介电磷玻璃及其制备方法、应用 (Low-dielectric phosphorus glass and preparation method and application thereof ) 是由 周毅 张成霞 白伟 郑浩 赵杉杉 同阳 杨峻宇 赵红星 王凯悦 秦梅 田玉明 于 2021-02-05 设计创作，主要内容包括：本发明提供一种低介电磷玻璃,所述磷玻璃组成按照摩尔%为：43.5-66.5%的P-2O-5,8-20%的BaO,8-20%的TiO-2,8-16%的Na-2O,0-9%的B-2O-3,0-2%的CaO,0-2%的MgO,0-2%的SrO,0-2%的ZnO,0-2%的Li-2O,0-2%的K-2O。本发明磷玻璃材料具有在高频场强下更低的介电常数与介电损耗,同时具有优良力学性能、热性能与低熔温特性。本发明磷玻璃材料适用于实现电子与微电子电路基板的低能耗制造、电子与微电子元器件的电子级无机封装与电子级玻纤生产的连续化与简易化生产等应用领域。(The invention provides low-dielectric phosphorus glass, which comprises the following components in percentage by mol: 43.5-66.5% of P 2 O 5 8-20% of BaO and 8-20% of TiO 2 8-16% of Na 2 O, 0-9% of B 2 O 3 0-2% of CaO, 0-2% of MgO, 0-2% of SrO, 0-2% of ZnO and 0-2% of Li 2 O, 0-2% of K 2 And O. The phosphorus glass material has lower dielectric constant and dielectric loss under high-frequency field intensity, and simultaneously has excellent mechanical property, thermal property and low melting temperature. The phosphorus glass material is suitable for realizing low-energy-consumption manufacturing of electronic and microelectronic circuit substrates and electronic grade inorganic packaging and electronic grade of electronic and microelectronic componentsThe continuous and simple production of glass fiber production and other application fields.)

1. A low dielectric phosphorus glass is characterized in that: the low-dielectric-phosphorus glass comprises the following components in percentage by mol: 43.5-66.5% of P₂O₅8-20% of BaO and 8-20% of TiO₂8-16% of Na₂O, 0-9% of B₂O₃0-2% of CaO, 0-2% of MgO, 0-2% of SrO, 0-2% of ZnO and 0-2% of Li₂O, 0-2% of K₂O。

2. The low dielectric phosphorus glass of claim 1, wherein: the low-dielectric phosphorus glass is prepared at room temperature of 25 ℃: at 1MHz, the dielectric constant is 4.008-6.306, and the dielectric loss is 2.8-6.1 × 10^-3To (c) to (d); at 10MHz, the dielectric constant is 3.816-6.074, and the dielectric loss is 7.2-23 × 10^-4To (c) to (d); dielectric constant at 100MHzBetween 3.701 and 5.835, the dielectric loss is 2.3-5.1 × 10^-4In the meantime.

3. The low dielectric phosphorus glass of claim 1, wherein: the low dielectric phosphorus glass has Vickers hardness of between 602 and 685MPa, Knoop hardness of between 505 and 573MPa, and fracture toughness of between 1.31 and 1.81 Pa.m at room temperature^1/2In the meantime.

4. The low dielectric phosphorus glass of claim 1, wherein: the transition temperature of the low-dielectric-constant phosphorus glass is between 467 ℃ and 521 ℃.

5. The low dielectric phosphorus glass of claim 1, wherein: the thermal conductivity of the low-dielectric phosphorus glass at room temperature and 25 ℃ is more than 1.3W/m.K.

6. A preparation method of low dielectric phosphorus glass is characterized by comprising the following steps: the method comprises the following steps: the low dielectric phosphorus glass of claim 1, wherein the raw materials are melted at 1150-1250 ℃ for 1-2h, then quickly molded in a preheated stainless steel mold, annealed at 450-500 ℃ for 2-3h to remove internal stress of the glass sheet, and cut and polished.

7. The method of claim 6, wherein the raw material is selected from the group consisting of phosphates, boric acids, carbonates, fluorides, and chlorides of the respective elements corresponding to the constituent oxides.

8. Use of the low dielectric phosphorus glass of claim 1 in low energy consumption fabrication of electronic and microelectronic circuit substrates, electronic grade inorganic packaging of electronic and microelectronic components, and continuous and simplified production of electronic grade glass fibers.

Technical Field

The invention relates to a glass with low melting temperature and low dielectric property, which has excellent force, heat and electrical properties and is suitable for the industries of electronics and microelectronic integrated circuits.

Background

With the rapid development of modern society and the increase of information technology demand of human society, electronic and microelectronic technologies are also rapidly developing, and further, the progress of miniaturization of electronic and microelectronic elements and high integration of electronic and microelectronic circuits is promoted. However, as the integration level increases, the problems of capacitance effect, thermal effect, interconnection delay, etc. on the integrated circuit board are also increased. There is a need to develop dielectric materials with good electrical characteristics at high frequency electric fields to meet the material requirements of highly integrated circuits.

Glass materials are favored in the fields of integrated circuits and microelectronics because of their good insulating properties, gas tightness, environmental stability, and ease of realization of large-scale fabrication. At present, the more applied low dielectric glass materials comprise two major products of D glass and E glass. But since they are based on SiO₂As a component for forming a glass network, its melting temperature>1400 ℃ is higher, which causes a series of problems of high production energy consumption, poor processing performance and the like, and further limits the development of the method in the aspects of large-scale, continuous and simplified production and the like in the manufacture of integrated circuit substrates.

Disclosure of Invention

The invention aims to provide a phosphorus glass material with low melting temperature and low dielectric property, and simultaneously has good mechanical and thermal properties.

The invention relates to low dielectric phosphorus glass, which comprises the following components in percentage by mol: 43.5-66.5% of P₂O₅8-20% of BaO and 8-20% of TiO₂8-16% of Na₂O, 0-9% of B₂O₃0-2% of CaO, 0-2% of MgO, 0-2% of SrO, 0-2% of ZnO and 0-2% of Li₂O, 0-2% of K₂O。

Further, the low dielectric phosphorus glass is prepared at room temperature of 25 ℃: at 1MHz, the dielectric constant is 4.008-6.306, and the dielectric loss is 2.8-6.1 × 10^-3To (c) to (d); at 10MHz, the dielectric constant is 3.816-6.074, and the dielectric loss is 7.2-23 × 10^-4To (c) to (d); at 100MHz, the dielectric constant is 3.701-5.835, and the dielectric loss is 2.3-5.1 × 10^-4In the meantime.

Furthermore, the Vickers hardness of the low-dielectric phosphorus glass at room temperature is between 602-685MPa, the Knoop hardness is between 505-573MPa, and the fracture toughness is between 1.31-1.81 Pa.m^1/2In the meantime.

Further, the transition temperature of the low dielectric phosphorus glass is between 467 ℃ and 521 ℃.

Furthermore, the thermal conductivity of the low dielectric phosphorus glass at room temperature of 25 ℃ is more than 1.3W/K.m.

The invention relates to a preparation method of low dielectric phosphorus glass, which comprises the following steps: according to the component proportion range of the low dielectric phosphorus glass, the raw materials which are weighed and uniformly mixed are placed in a high-purity corundum or platinum crucible, are melted at the temperature of 1150-1250 ℃ for 1-2h and then are quickly poured into a preheated stainless steel mold to be quickly molded, then are annealed at the temperature of 450-500 ℃ for 2-3h to remove the internal stress of a glass sheet, and the glass sheet with the internal stress removed is cut and polished.

The invention relates to low dielectric phosphorus glass, which is prepared from phosphate, boric acid, carbonate, fluoride, chloride and other components of elements corresponding to oxides.

The invention has the beneficial effects that: the low dielectric phosphorus glass has lower dielectric constant and dielectric loss under high frequency, low melting temperature, low transformation temperature and good mechanical and heat conduction performance, thereby achieving the purposes of reducing production energy consumption and realizing continuous and simplified production of electronic and microelectronic integrated circuit substrate manufacturing, electronic grade inorganic packaging and electronic grade glass fiber production.

Detailed Description

The inventor of the invention obtains the phosphorus glass material with low melting temperature and low dielectric property by repeated experiments and researches to obtain specific components and lower cost. The components involved in the present invention are explained below. Unless otherwise specified, the contents of the respective components are all expressed in terms of mole percentages of the respective components converted to oxides in the present specification. The "components converted to oxides" means that when all of phosphates, boric acids, carbonates, oxides, etc. used as raw materials of the phosphorus glass composition of the present invention are decomposed and converted to oxides at the time of melting, the total molar amount of oxides containing the elements is 100%.

P₂O₅Is an important component of the network structure of the glass material, when P₂O₅When the content is less than 43.5%, the dielectric constant and loss are greatly increased, and when P is contained₂O₅When the content is more than 66.5%, the melting temperature of the glass is increased and devitrification and phase separation of the glass easily occur.

B₂O₃Is a modifier of a glass network framework and has good fluxing effect, and when the content is higher than 9 percent, the low dielectric property is deteriorated.

BaO contributes to the improvement of the low-temperature melting property of the glass, but when the content is less than 8%, the melting temperature is still high, and when the content is more than 20%, the glass devitrification is also improved.

TiO₂Is a component which contributes to lowering the melting temperature of the glass and improving the durability, and when the content is less than 8%, the melting temperature is not significantly lowered, and when the content is more than 20%, the phase separation of the glass is likely to occur.

Na₂O is to increase the low temperature of the glassThe melting and forming components, but if the content is more than 16%, the dielectric constant and loss of the glass are increased, and if the content is less than 8%, the effect of lowering the melting temperature is not good.

Li₂O and K₂O can improve the low-temperature melting property and the formability of the glass, but when the amount of O is more than 2%, both the dielectric constant and the loss are increased.

MgO, CaO, SrO and ZnO contribute to lowering the viscosity of the glass and improving the low-temperature meltability, but their content exceeding 2% causes devitrification of the glass.

In the phosphorus glass system of the present invention, as the glass composition, only the above-mentioned components may be used, but other components such as Sb may be added within a range not seriously affecting the properties₂O₃、Bi₂O₃、As₂O₃、F^-、Cl^-And the like.

Examples 1-20 (tables 1 and 2) of the present invention phosphorus glasses were made using the following melt-and-quench method: the raw materials such as oxide, phosphate, carbonate, fluoride, chloride and the like which are weighed and uniformly mixed are placed in a high-purity corundum or platinum crucible according to the component proportion range, are melted at the temperature of 1150-1250 ℃ for 1-2h and then are quickly poured into a preheated stainless steel mold for quick molding, and then are annealed at the temperature of 450-500 ℃ for 2-3h to remove the internal stress of the glass sheet, and the glass sheet with the internal stress removed is cut and polished.

In the examples, the dielectric properties of the phosphorus glass were measured by an Agilent 4294 precision impedance analyzer, and the samples were tested by GB/T16822-1997 test method for dielectric properties of dielectric crystals, with the specification of 10mm × 10mm × 0.6-0.8 mm.

In the embodiment, the hardness and the fracture toughness of the phosphorus glass are measured by a 401MVAS-P type microcomputer precision hardness tester, the specification of a sample is 10mm multiplied by 0.8-1mm, and the test is carried out by a small load Vickers hardness indentation method of GB/T37900-.

In the examples, the melting temperature Tm of the phosphorus glass is determined by the temperature at which the melt is completely fluid when the mixture is heated in a crucible by a shaking methodAnd (4) determining. The transition temperature Tg of the phosphorus glass was METTLER TGA/DSC 3⁺And (4) measuring by using a comprehensive thermal analyzer.

Thermal conductivity of phosphorus glass in examples was measured using an LW9389 thermal conductivity tester, with a sample specification of 25 mm. times.25 mm. times.1-2 mm, in accordance with ASTM C518-2010.

TABLE 1

TABLE 2

The phosphorus glass has the characteristics of low dielectric constant and low dielectric loss under a high-frequency electric field, has good mechanical and thermal properties, and lower melting temperature and transition temperature, and is suitable for the fields of low-energy-consumption manufacturing of communication and microelectronic circuit substrates, low-power-consumption inorganic packaging of electronic and microelectronic components, low-power-consumption continuous and simplified production of electronic-grade glass fibers and the like.