CN114671614A - A kind of low dielectric and low loss calcium aluminum borosilicate glass-ceramic material and preparation method - Google Patents

Abstract

The invention belongs to the field of electronic ceramics and its manufacture, and relates to a low-dielectric and low-loss calcium-aluminum-borosilicate-based glass-ceramic material and a preparation method thereof. In the present invention, the raw material components and proportions of the calcium borosilicate-based glass-ceramic material are greatly adjusted, and finally calcium, aluminum, boron and silicon are used as the base materials, BaCO ₃ and P ₂ O ₅ are supplemented, and CeO is added in a small amount. _2. As trace elements, La ₂ O ₃ and Na ₂ CO ₃ can be sintered at a low temperature of 850～950℃ to obtain low intermediary ( _εr =4～5) by melting the raw materials, water quenching, granulation and other processes. , Low loss (Tanδ<0.0006) glass-ceramic material. It has high signal transmission speed, which greatly reduces power consumption; low sintering temperature (850 ℃ ~ 950 ℃), can well co-fire with low-resistivity silver electrodes, suitable for manufacturing low-temperature co-fired multi-layer ceramic substrates, satisfying The process conditions of LTCC are required, and the performance is better, which provides a better choice for the needs of high-speed circuits.

Description

A kind of low dielectric and low loss calcium aluminum borosilicate glass-ceramic material and preparation method

technical field

The invention belongs to the field of electronic ceramics and its manufacture, and relates to a low dielectric constant and low dielectric loss calcium-aluminum borosilicate-based glass-ceramic material and a preparation method thereof.

Background technique

As electronic products have higher and higher requirements for various properties of the packaging substrates used, the packaging substrates have great research value. Electronic product manufacturers have to work hard to develop a new advanced integration, packaging, interconnection technology. Low Temperature Co-Fired Ceramic (LTCC) technology came into being. LTCC technology is a subversive process technology proposed by Hughes Company in the United States in the mid-1980s that can co-fire multi-layer substrates. (<950°C) co-firing with metal conductors (Ag, Au) with low melting point and high conductivity, and the whole process is less difficult, which greatly improves the operating performance of various electronic devices and the reliability of components.

At present, LTCC technology has been industrialized in developed countries such as Japan and the United States. However, the technology is still in its infancy in China, and there are few independent intellectual property rights in materials, systems and equipment. my country urgently needs to develop a series of LTCC ceramic materials and substrate products with independent intellectual property rights. Low-dielectric constant ceramic materials sintered at low temperature can be divided into three categories: glass-ceramic (also called glass-ceramic), glass-ceramic filler composite system and amorphous glass system. In recent years, a lot of research has been done on glass-ceramics, and many glasses with low dielectric constant systems have been developed. Glass-ceramic is a composite material with uniform distribution of microcrystals and glass phases, and a glass network structure composed of boron and silicon. Many glass-ceramics for LTCC are based on borosilicate glasses, such as CaO-B2O3 _{- SiO2} glass _- ceramics.

Chinese invention _patent (application _{number 201110051412.4 )} , a glass _- ceramic material for electronic substrates was _invented by the University of Electronic Science and Technology of _China . The distribution ratio is CaCO ₃ 33-50 mol%, B ₂ O ₃ 12-30 mol %, SiO ₂ 30-50 mol %, ZnO 0-2 mol %, P ₂ O ₅ 0-2 mol %, TiO ₂ 0-2 mol %, ZrO ₂ 0～2mol%. The preparation method of the glass-ceramic material adopts traditional glass technology, and the finally prepared glass-ceramic has low dielectric constant (6.0-7.2, 1MHz) and low dielectric loss (tg<0.003, 1MHz) and low sintering temperature (850-950 ℃), in line with LTCC technical requirements.

However, with the advent of the 5G era, electronic products have higher and higher requirements on the performance of packaging substrates. When facing the low signal delay requirements of high-speed circuits, we need to reduce the dielectric and electrical loss properties of materials as much as possible.

SUMMARY OF THE INVENTION

In view of the above problems or deficiencies, the present invention provides a low-dielectric and low-loss calcium-aluminum-borosilicate-based glass-ceramic material and a preparation method, so as to meet the current industry requirements for lower dielectric constant and lower dielectric of electronic substrate LTCC materials loss demand.

A low-dielectric and low-loss calcium-aluminum-borosilicate-based glass-ceramic material, whose raw material components are: 18-28 mol% CaCO ₃ , 18-28 mol % B ₂ O ₃ , 15-20 mol % SiO ₂ , 11-28 mol % 25mol% of Al ₂ O ₃ , 8-12mol% of BaCO ₃ , 5-8mol% of P ₂ O ₅ and 0-6mol% of trace elements; the proportion of trace elements does not take 0, specifically: 0-3mol% of CeO ₂ , 0-3 mol % La ₂ O ₃ and/or 0-3 mol % Na ₂ CO ₃ . It is obtained by melting, water quenching, granulation and sintering in sequence.

Its dielectric constant ε _r =4～5, dielectric loss Tanδ<0.0006, with high signal transmission speed, greatly reducing power consumption; sintering temperature is 850℃～950℃.

The preparation method of the above-mentioned low-dielectric and low-loss calcium-aluminum-borosilicate-based glass-ceramic material is as follows:

Step 1: Prepare raw materials CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , CeO ₂ , La ₂ O ₃ and Na ₂ CO ₃ according to the formula.

The raw material formula is: 18-28 mol% of CaCO ₃ , 18-28 mol % of B ₂ O ₃ , 15-20 mol % of SiO ₂ , 11-25 mol % of Al ₂ O ₃ , 8-12 mol % of BaCO ₃ , 5- 8mol% of _P2O5 and _0-6mol % of trace elements. The proportion of trace elements does not take 0, specifically: 0-3 mol% of CeO ₂ , 0-3 mol% of La ₂ O ₃ and/or 0-3 mol% of Na ₂ CO ₃ .

Step 2: Ball mill all the powders prepared in Step 1 with zirconium balls and deionized water and dry them.

Step 3: The dried powder obtained in Step 2 is heated to 1400-1500° C. for heat preservation to melt and homogenize.

Step 4: Water-quench the melted and homogenized melt obtained in Step 3 to obtain broken glass bodies.

Step 5: The broken glass body obtained in Step 4 is ball-milled and then dried to obtain glass powder.

Step 6: The glass powder obtained in Step 5 is granulated, and after being pressed and formed, the glass-ceramic material is obtained by sintering at 850-950° C. and keeping the temperature for 0.5-1 hour.

Further, the drying temperature in step 2 is 80°C to 110°C.

Further, after the glass powder in the step 6 is pressed and formed, the glue is removed first and then sintered for heat preservation.

In the present invention, the raw material components and proportions of the calcium borosilicate-based glass-ceramic material are greatly adjusted, and finally calcium, aluminum, boron and silicon are used as the base materials, BaCO ₃ and P ₂ O ₅ are supplemented, and CeO is added in a small amount. _2. La ₂ O ₃ and Na ₂ CO ₃ are used as trace elements, and low dielectric and low loss glass-ceramics can be obtained by sintering at a low temperature of 850-950 ° C by melting raw materials, water quenching, granulation and other processes. Material. It is suitable for the process conditions of LTCC and has better performance, providing a better choice for the needs of high-speed circuits.

The glass-ceramic material prepared by the present invention has the following characteristics:

1. Low dielectric constant (ε _r =4~5), low dielectric loss (Tanδ<0.0006), high signal transmission speed, and greatly reduced power consumption.

2. The sintering temperature is low (850℃～950℃), which can co-fire well with the low resistivity silver electrode, and is suitable for the manufacture of low-temperature co-fired multilayer ceramic substrates.

Description of drawings

FIG. 1 is the XRD diffraction pattern of the samples of Examples 1-4.

Detailed ways

The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

Example 1

In molar ratios CaCO ₃ (28 mol %), Al ₂ O ₃ (11 mol %), B ₂ O ₃ (28 mol %), SiO ₂ (15 mol %), BaCO ₃ (10 mol %), P ₂ O ₅ (5 mol %) , CeO ₂ (3mol%) is converted to obtain the amount of powder, and CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , CeO ₂ are accurately weighed according to the calculated amount. Ball mill with the ratio of material ball to water 1:5:1.5, put into corundum crucible after drying, melt glass (1400 ℃, heat preservation for 1h), quench the molten glass with water to obtain transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), dry pressing under 20MPa pressure to form green sheets. After debinding at 450° C., the obtained green sheet was heated to 950° C. for sintering and kept for 30 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Example 2

In molar ratios CaCO ₃ (28 mol %), Al ₂ O ₃ (11 mol %), B ₂ O ₃ (28 mol %), SiO ₂ (15 mol %), BaCO ₃ (10 mol %), P ₂ O ₅ (5 mol %) , CeO ₂ (3mol%) is converted to obtain the amount of powder, and CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , CeO ₂ are accurately weighed according to the calculated amount. Ball milled at a ratio of 1:5:1.5 of material-to-ball to water, dried and put into a corundum crucible, melted into glass (1400 ° C, heat preservation for 2 h), and water-quenched the molten glass to obtain a transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), dry pressing under 20MPa pressure to form green sheets. The obtained green sheet was degummed at 450°C, then heated to 850°C for sintering and kept for 30 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Example 3

In molar ratios CaCO ₃ (20 mol %), Al ₂ O ₃ (17 mol %), B ₂ O ₃ (23 mol %), SiO ₂ (17 mol %), BaCO ₃ (12 mol %), P ₂ O ₅ (5 mol %) , CeO ₂ (3 mol%), Na ₂ CO ₃ (3 mol %) are converted to obtain the amount of powder, and according to the calculated amount, accurately weigh CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , CeO ₂ , Na ₂ CO ₃ . Ball mill with the ratio of material ball to water 1:5:2, put into corundum crucible after drying, melt glass (1400 ℃, heat preservation 2h), quench the molten glass with water to obtain transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), dry pressing under 20MPa pressure to form green sheets. After debinding at 450°C, the obtained green sheet was heated to 900°C for sintering and kept for 60 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Example 4

In molar ratios CaCO ₃ (20 mol %), Al ₂ O ₃ (17 mol %), B ₂ O ₃ (23 mol %), SiO ₂ (17 mol %), BaCO ₃ (12 mol %), P ₂ O ₅ (5 mol %) , La ₂ O ₃ (3mol%), Na ₂ CO ₃ (3mol%) are converted to obtain the amount of powder, and accurately weigh CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO according to the calculated amount _3. P ₂ O ₅ , La ₂ O ₃ , Na ₂ CO ₃ . Ball mill with the ratio of material ball to water 1:5:2, put into corundum crucible after drying, melt glass (1450 ℃, heat preservation 2h), quench the molten glass with water to obtain transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), it is dry-pressed under 20MPa pressure. After debinding at 450°C, the green sheet was heated to 900°C for sintering and kept for 60 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Example 5

In molar ratios CaCO ₃ (18 mol %), Al ₂ O ₃ (25 mol %), B ₂ O ₃ (18 mol %), SiO ₂ (18 mol %), BaCO ₃ (10 mol %), P ₂ O ₅ (8 mol %) , La ₂ O ₃ (3mol%) is converted to obtain the amount of powder, and accurately weigh CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , La ₂ according to the calculated amount O ₃ . Ball mill with the ratio of material ball to water 1:5:2.5, put into corundum crucible after drying, melt glass (1450 ℃, heat preservation 2h), quench the molten glass with water to obtain transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), dry pressing under 20MPa pressure to form green sheets. After debinding at 450°C, the obtained green sheet was heated to 900°C for sintering and kept for 60 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Example 6

In molar ratios CaCO ₃ (18 mol %), Al ₂ O ₃ (25 mol %), B ₂ O ₃ (18 mol %), SiO ₂ (20 mol %), BaCO ₃ (8 mol %), P ₂ O ₅ (8 mol %) , La ₂ O ₃ (3mol%) is converted to obtain the amount of powder, and accurately weigh CaCO ₃ , Al ₂ O ₃ , B ₂ O ₃ , SiO ₂ , BaCO ₃ , P ₂ O ₅ , La ₂ according to the calculated amount O ₃ . Ball mill with the ratio of material ball to water 1:5:2.5, put into corundum crucible after drying, melt glass (1500 ℃, heat preservation 3h), quench the molten glass with water to obtain transparent broken glass body. The broken glass body is subjected to wet ball milling (with deionized water and zirconium balls as the medium for 2 hours) and then dried to obtain glass powder. After granulation (glass powder and 40% acrylic acid), dry pressing under 20MPa pressure to form green sheets. After debinding at 450° C., the obtained green sheet was heated to 950° C. for sintering and kept for 30 minutes to obtain glass-ceramics. The properties are shown in Table 1.

Table 1 Properties of sintered samples in each case

Figure 1 shows the XRD diffraction patterns of the ceramic material of the present invention after being kept at the optimum sintering temperature for 4 hours, corresponding to samples Nos. 1 to 4 of the embodiment respectively. It can be seen from FIG. 1 that the main crystal phase of Examples 1 and 2 is CaAl ₂ B ₂ O ₇ (ICSD 00-019-0205). The main crystal phase of Examples 3 and 4 was CaAl ₂ (BO ₃ ) ₂ O (ICSD 01-089-5563). The grains of CaAl ₂ B ₂ O ₇ are elongated and dense, and the more crystals there are, the better the dielectric properties of the material.

It can be seen from the above examples that the present invention greatly adjusts the raw material components of the calcium borosilicate-based glass-ceramic material, and finally uses calcium, aluminum, boron and silicon as the base materials, supplemented by BaCO ₃ and P ₂ O ₅ , And trace addition of CeO ₂ , La ₂ O ₃ and Na ₂ CO ₃ as trace elements, through the traditional process of melting raw materials, water quenching, granulation, etc., can be sintered at a low temperature of 850 ~ 950 ℃ to obtain low dielectric (ε) _r =4～5), low loss (Tanδ<0.0006) glass-ceramic material. Not only the power consumption is greatly reduced, but also it can co-fire well with the low-resistivity silver electrode, which is suitable for the process conditions of LTCC and has better performance, providing a better choice for the needs of high-speed circuits.

Claims (4)

1. A low-dielectric low-loss calcium-aluminum-boron-silicon-based glass-ceramic material is characterized in that:

the raw material components are as follows: 18 to 28 mol% of CaCO₃18 to 28 mol% of B₂O₃15 to 20 mol% of SiO₂11 to 25 mol% of Al₂O₃8 to 12 mol% of BaCO₃5 to 8 mol% of P₂O₅And 0-6 mol% of trace elements; the proportion of the trace elements is not 0, and specifically comprises the following components: 0 to 3 mol% of CeO₂0 to 3 mol% of La₂O₃And/or 0 to 3 mol% of Na₂CO₃(ii) a Sequentially carrying out melting, water quenching, granulation molding and sintering to obtain the material;

its dielectric constant ε_r4-5, dielectric loss Tan delta<0.0006 and the sintering temperature is 850-950 ℃.

2. The method for preparing the low dielectric low loss calcium aluminoborosilicate silicon based microcrystalline glass material of claim 1, comprising the steps of:

step 1: raw material CaCO₃、Al₂O₃、B₂O₃、SiO₂、BaCO₃、P₂O₅、CeO₂、La₂O₃And Na₂CO₃Preparing materials according to a formula;

the formula of the raw materials is as follows: CaCO₃18～28mol％、B₂O₃ 18～28mol％、SiO₂15～20mol％、Al₂O₃ 11～25mol％、BaCO₃ 8～12mol％、P₂O₅5-8 mol% and 0-6 mol% of trace elements; the proportion of the trace elements is not 0, and specifically comprises the following components: CeO (CeO)₂ 0～3mol％、La₂O₃0 to 3 mol% and/or Na₂CO₃0～3mol；

Step 2: ball-milling and drying all the powder prepared in the step 1 with zirconium balls and deionized water;

and step 3: heating the dried powder obtained in the step 2 to 1400-1500 ℃, and preserving heat for melting homogenization;

and 4, step 4: water quenching the melt obtained in the step 3 to obtain a cullet;

and 5: ball-milling the crushed glass body obtained in the step (4) and drying to obtain glass powder;

and 6: and (4) granulating the glass powder obtained in the step (5), pressing and forming, sintering at 850-950 ℃, and keeping the temperature for 0.5-1 hour to obtain the glass ceramic material.

3. The method of claim 2 for preparing a low dielectric low loss calborosilicate based microcrystalline glass material, wherein: the drying temperature of the step 2 is 80-110 ℃.

4. The method of claim 2 for preparing a low dielectric low loss calborosilicate based microcrystalline glass material, wherein: and (6) after the glass powder is formed by pressing, removing the glue, and then sintering and preserving the heat.

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