CN112723737B - Low-dielectric phosphorus glass and preparation method and application thereof - Google Patents
Low-dielectric phosphorus glass and preparation method and application thereof Download PDFInfo
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- CN112723737B CN112723737B CN202110159988.6A CN202110159988A CN112723737B CN 112723737 B CN112723737 B CN 112723737B CN 202110159988 A CN202110159988 A CN 202110159988A CN 112723737 B CN112723737 B CN 112723737B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/15—Ceramic or glass substrates
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Abstract
The invention provides 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 K2And 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 the application fields of low-energy-consumption manufacturing of electronic and microelectronic circuit substrates, electronic grade inorganic packaging of electronic and microelectronic components, continuous and simplified production of electronic grade glass fiber production and the like.
Description
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.
Further, theThe 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.m1/2In 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 a component for improving the low-temperature melting property and the formability of the glass, but if the content is more than 16%, the dielectric constant and the 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-.
The melting temperature Tm of the phosphorus glass in the examples is determined by the temperature at which the melt is completely fluid when the mixture is heated in the crucible by the shaking method. 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.
Claims (6)
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 K2At 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 × 10-4The transition temperature of the low-dielectric-constant phosphorus glass is between 467 ℃ and 521 ℃.
2. 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 MPa-m at room temperature1/2In the meantime.
3. 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.
4. 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.
5. The method of claim 4, 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.
6. 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.
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Citations (6)
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|---|---|---|---|---|
| JPS6136137A (en) * | 1984-07-26 | 1986-02-20 | Matsushita Electric Works Ltd | Low-melting point glass composition |
| JPS61151042A (en) * | 1984-12-22 | 1986-07-09 | Matsushita Electric Works Ltd | Glass composition having low melting point |
| CN1524816A (en) * | 2002-12-27 | 2004-09-01 | Hoya株式会社 | Optical glass, preform for press molding and optical element |
| CN101186439A (en) * | 2007-12-05 | 2008-05-28 | 成都光明光电股份有限公司 | High-refraction high-dispersion phosphate optical glass and heat treating method thereof |
| CN103030299A (en) * | 2012-12-18 | 2013-04-10 | 沈阳化工大学 | P2O5-BaO-Na2O-K2O-Y2O3-Eu2O3 glass ceramic and preparation method thereof |
| JP2017095286A (en) * | 2014-02-25 | 2017-06-01 | 東罐マテリアル・テクノロジー株式会社 | Glaze for aluminum enamel |
-
2021
- 2021-02-05 CN CN202110159988.6A patent/CN112723737B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6136137A (en) * | 1984-07-26 | 1986-02-20 | Matsushita Electric Works Ltd | Low-melting point glass composition |
| JPS61151042A (en) * | 1984-12-22 | 1986-07-09 | Matsushita Electric Works Ltd | Glass composition having low melting point |
| CN1524816A (en) * | 2002-12-27 | 2004-09-01 | Hoya株式会社 | Optical glass, preform for press molding and optical element |
| CN101186439A (en) * | 2007-12-05 | 2008-05-28 | 成都光明光电股份有限公司 | High-refraction high-dispersion phosphate optical glass and heat treating method thereof |
| CN103030299A (en) * | 2012-12-18 | 2013-04-10 | 沈阳化工大学 | P2O5-BaO-Na2O-K2O-Y2O3-Eu2O3 glass ceramic and preparation method thereof |
| JP2017095286A (en) * | 2014-02-25 | 2017-06-01 | 東罐マテリアル・テクノロジー株式会社 | Glaze for aluminum enamel |
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