CN111908797B - Low-thermal-expansion cordierite-based microcrystalline glass material and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of electronic ceramic materials, and provides a low thermal expansion cordierite-based glass-ceramic material and a preparation method thereof, which are used for ultra-large-scale integrated circuit packaging. The glass-ceramic material of the present invention is composed of: 15-19wt% of MgO, 26-30wt% of _Al2O3 , _46-50wt % of _SiO2 , _2-6wt % of ZrO2, _2-6wt % _of B2O3 1-5wt%, K ₂ O is 1-3wt%; by introducing K ₂ O as modifier, ZrO ₂ as crystal nucleating agent, and B ₂ O ₃ as calcination reducing agent, a part of (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase is transformed into Mg ₂ Al ₄ Si ₅ O ₁₈ phase, thereby adjusting the thermal expansion coefficient to tend to Si chip (3.5×10 ^‑6 /℃), and can be adjusted at 2.5～3.5×10 ^‑6 /℃, thermal stability Good; at the same time, the flexural strength can reach 150～200MPa, the Young’s modulus can reach 80～95GPa, the dielectric constant is 5～6(@1MHz), and the dielectric loss is 0.5～1×10 ^‑3 (@1MHz), It can improve the signal transmission speed and greatly reduce the power consumption. In conclusion, the low thermal expansion cordierite-based glass-ceramic material of the present invention is suitable for VLSI packaging, can significantly reduce signal transmission delay, reduce power consumption, and is compatible with silicon chips. match.

Description

A kind of low thermal expansion cordierite-based glass-ceramic material and preparation method thereof

technical field

The invention belongs to the field of electronic ceramic materials, and relates to a low thermal expansion cordierite-based glass-ceramic material and a preparation method thereof; it is particularly suitable for ultra-large-scale integrated circuit packaging.

Background technique

In recent years, the rapid development of information technology has promoted the ultra-large scale and multi-functionalization of integrated circuits, and the search for packaging materials with excellent performance has become the focus of attention; MgO-Al ₂ O ₃ -SiO ₂ series glass-ceramics have a low thermal expansion coefficient. , excellent dielectric properties and other characteristics, but there are problems such as poor mechanical properties and high sintering temperature.

For example, Journal of Non-Crystalline Solids, 2015, 419: 16-26 reported the effect of K ₂ O on the properties of magnesium-aluminum-silicon-based glass-ceramics. Al ₂ O ₃ is 21.61 mol%, SiO ₂ is 54.00 mol%, and K ₂ O is 2.79 mol%; the mixture is melted and kept at 1550℃ for 6h, granulated with PVA and sintered at 925℃ for 6h. It has the best performance; its flexural strength is 145MPa, its thermal expansion coefficient is 5.63×10 ^-6 /℃, its dielectric constant is 7.51 (@10MHz), and its dielectric loss is 14×10 ^-3 (@10MHz). The bending strength is low, and the thermal expansion coefficient and dielectric loss are high.

In view of the above problems, the inventor of the present invention disclosed "a cordierite-based glass-ceramic material and its preparation method" in the invention patent with application number 201810507515.9. 20wt%, Al ₂ O ₃ is 25-35wt%, SiO ₂ is 40-50wt%, ZrO ₂ is 5-10wt%, B ₂ O ₃ is 1-5wt%; the mixture is melted and kept at 1400-1450 ℃ for 1- 2h, granulated with acrylic acid and sintered at 875～925℃ for 1～2h, the final obtained material has the following properties: flexural strength of 160～230MPa, Young's modulus of 80～100GPa, dielectric constant of 4.5～ 5.0(@1MHz), the dielectric loss is 0.5～0.6×10 ^-3 (@1MHz), and the thermal expansion coefficient is 1.5～2.5×10 ^-6 /℃; Good thermal match with silicon chips.

SUMMARY OF THE INVENTION

The present invention provides a low thermal expansion cordierite-based microcrystal in order to solve the problems of poor mechanical properties, mismatched thermal expansion coefficients, large dielectric loss, etc. in existing ceramic materials in the background technology, resulting in large signal transmission delay and high power consumption. The glass material and the preparation method thereof can not only achieve good thermal matching with the silicon chip, but also have high flexural strength and Young's modulus, and have excellent dielectric properties.

To achieve the above object, the technical scheme adopted in the present invention is:

A low thermal expansion cordierite-based glass-ceramic material and a preparation method thereof, characterized in that, according to mass percentage, the composition is as follows:

MgO is 15-19wt%,

Al ₂ O ₃ is 26 to 30 wt %,

SiO ₂ is 46-50wt%,

ZrO ₂ is 2 to 6wt%,

B ₂ O ₃ is 1 to 5 wt %,

K ₂ O is 1 to 3 wt %.

The above-mentioned low thermal expansion cordierite-based glass-ceramic material and preparation method thereof, comprising the following steps:

Step 1: Design a formula with MgO, Al ₂ O ₃ , SiO ₂ , ZrO ₂ , B ₂ O ₃ , and K ₂ O as components, calculate the actual amount of the corresponding raw materials of each oxide according to the ratio, and mix them evenly;

Step 2: dry after ball milling for 2 to 4 hours, place the mixture in a crucible, melt at a high temperature of 1400 to 1450 ° C for 1 to 2 hours, and pour it into deionized water to obtain transparent glass slag;

Step 3: Ball milling the obtained glass slag in a ceramic jar for 1-1.5 hours, and drying to obtain glass powder;

Step 4: ball mill the obtained glass powder in a nylon tank for 6 to 8 hours, and obtain a uniformly dispersed powder after drying;

Step 5: adding acrylic acid to the powder for granulation, and after dry pressing, sintering at 900-950° C. and keeping the temperature for 1-2 hours to obtain low thermal expansion cordierite-based glass-ceramic.

Compared with the prior art, the beneficial effects of the present invention are embodied in:

The invention provides a low thermal expansion cordierite-based glass-ceramic material, which belongs to a magnesium-aluminum-silicon system. By introducing K ₂ O as a modifier, ZrO ₂ as a crystal nucleating agent, and B ₂ O ₃ as a calcination reducing agent, a part of the The (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase is transformed into the Mg ₂ Al ₄ Si ₅ O ₁₈ phase. By calculation, the content of the Mg ₂ Al ₄ Si ₅ O ₁₈ phase in the final material is 65.2-76.5%, (MgAl ₂ Si The content of ₃ O ₁₀ ) _0.6 phase is 18.3-25.7%; the thermal expansion coefficient of glass-ceramic is mainly determined by the type and content of crystal phase, because the thermal expansion coefficient of Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 1.5×10 ^-6 /℃ , the thermal expansion coefficient of (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase is about 5.0×10 ^-6 /℃, the content of different crystal phases will definitely change the thermal stress inside the material, thus adjusting the thermal expansion coefficient to the Si chip (3.5×10 ^-6 /℃), and adjustable at 2.5～3.5×10 ^-6 /℃, good thermal stability; at the same time, the flexural strength can reach 150～200MPa, the Young’s modulus can reach 80～95GPa, and the dielectric constant is low 5～6(@1MHz), the dielectric loss is low by 0.5～1×10 ^-3 (@1MHz), the signal transmission speed is improved, and the power consumption is greatly reduced; The VLSI package can significantly reduce signal transmission delay, reduce power consumption, and match well with silicon chips. In addition, the sintering temperature of the present invention is further reduced to below 950° C., energy consumption is reduced, and the preparation method has a simple technological process and abundant raw material sources, which is of great significance to industrialized production.

Description of drawings

1 is an XRD pattern of a low thermal expansion cordierite-based glass-ceramic of Example 2.

FIG. 2 is a SEM image of a section of a low thermal expansion cordierite-based glass-ceramic in Example 2. FIG.

Detailed ways

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

Example 1

According to the formula: MgO is 15wt%, Al ₂ O ₃ is 26wt%, SiO ₂ is 50wt%, ZrO ₂ is 6wt%, B ₂ O ₃ is 1wt%, K ₂ O is 2wt%, and the weight of the corresponding raw materials is accurately calculated , after accurate weighing, ball-milled for 2 hours to make it evenly mixed; after drying, the mixture was placed in a crucible and melted, heated to 1400 ° C for 1.5 hours, and then water-quenched after melting; then the obtained glass slag was subjected to wet ball milling , dried to obtain glass powder, ball-milled with deionized water as medium for 6 hours, and dried to obtain uniformly dispersed powder; after granulation and dry pressing, the powder was sintered at 900 ° C and kept for 1 hour to obtain low temperature Thermally expanded cordierite-based glass-ceramic material.

In the low thermal expansion cordierite-based glass-ceramic material prepared in this example, the content of the Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 73.4%, and the content of the (Mg Al ₂ Si ₃ O ₁₀ ) _0.6 phase is 19.1%. The performance indicators are: dielectric constant 5.54 (@1MHz), dielectric loss 0.75×10 ^-3 (@1MHz), thermal expansion coefficient 2.72×10 ^-6 /℃, flexural strength 175MPa, Young's modulus 92Gpa.

Example 2

According to the formula: MgO is 16wt%, Al ₂ O ₃ is 27wt%, SiO ₂ is 49wt%, ZrO ₂ is 5wt%, B ₂ O ₃ is 2wt%, K ₂ O is 1wt%, and the weight of the corresponding raw materials is accurately calculated , after accurate weighing, ball-milled for 2 hours to make it evenly mixed; after drying, the mixture was placed in a crucible and melted, heated to 1400 ° C for 2 hours, and water-quenched after melting was complete; then the obtained glass slag was subjected to wet ball milling , dried to obtain glass powder, ball milled with deionized water as medium for 6 hours, and dried to obtain uniformly dispersed powder; after granulation and dry pressing, the powder was sintered at 900 ° C and kept for 1.5 hours to obtain low Thermally expanded cordierite-based glass-ceramic material.

The XRD pattern of the low thermal expansion cordierite-based glass-ceramic material prepared in this example is shown in FIG. 1 , wherein the main crystalline phase is Mg ₂ Al ₄ Si ₅ O ₁₈ , and the secondary crystalline phase is (MgAl ₂ Si ₃ O ₁₀ ) _0.6 and ZrO ₂ ; the SEM image is shown in Figure 2, the darker area A is the crystalline phase, the bright area B is the glass phase, and the black area C is the hole, it can be seen that the crystalline phase has a higher proportion and fewer holes , so that the material has a low thermal expansion coefficient and high mechanical properties; more specifically, the content of the Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 65.2%, and the (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase has a content of 65.2%. The content is 25.7%. Various performance indicators are: dielectric constant 5.39 (@1MHz), electrical loss 0.63×10 ^-3 (@1MHz), thermal expansion coefficient 3.32×10 ^-6 /℃, flexural strength 196MPa, Young's modulus 95Gpa.

Example 3

According to the formula: MgO is 17wt%, Al ₂ O ₃ is 28wt%, SiO ₂ is 47wt%, ZrO ₂ is 4wt%, B ₂ O ₃ is 1wt%, K ₂ O is 3wt%, and the weight of the corresponding raw materials is accurately calculated , after accurate weighing, ball-milled for 3 hours to make it evenly mixed; after drying, the mixture was placed in a crucible and melted, heated to 1450 ° C for 1 hour, and water-quenched after melting was complete; then the obtained glass slag was subjected to wet ball milling , dried to obtain glass powder, ball-milled with deionized water as medium for 7 hours, and dried to obtain uniformly dispersed powder; after granulation and dry pressing, the powder was sintered at 925 ° C and kept for 1.5 hours to obtain low Thermally expanded cordierite-based glass-ceramic material.

In the low thermal expansion cordierite-based glass-ceramic material prepared in this example, the content of the Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 68.4%, and the content of the (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase is 22.6%. The performance indicators are: dielectric constant 5.43 (@1MHz), dielectric loss 0.77×10 ^-3 (@1MHz), thermal expansion coefficient 3.13×10 ^-6 /℃, flexural strength 173MPa, Young's modulus 90Gpa.

Example 4

According to the formula: MgO is 15wt%, Al ₂ O ₃ is 30wt%, SiO ₂ is 46wt%, ZrO ₂ is 3wt%, B ₂ O ₃ is 4wt%, K ₂ O is 2wt%, and the weight of the corresponding raw materials is accurately calculated , after accurate weighing, ball-milled for 4 hours to make it evenly mixed; after drying, the mixture was placed in a crucible and melted, heated to 1450 ° C for 1.5 hours, and then water-quenched after melting; then the obtained glass slag was subjected to wet ball milling , dried to obtain glass powder, ball-milled with deionized water for 8 hours, and dried to obtain uniformly dispersed powder; after granulation and dry pressing, the powder was sintered at 925 ° C and kept for 2 hours to obtain low Thermally expanded cordierite-based glass-ceramic material.

In the low thermal expansion cordierite-based glass-ceramic material prepared in this example, the content of Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 70.6%, and the content of (Mg Al ₂ Si ₃ O ₁₀ ) _0.6 phase is 21.5%. The performance indicators are: dielectric constant 5.62 (@1MHz), dielectric loss 0.86×10 ^-3 (@1MHz), thermal expansion coefficient 2.97×10 ^-6 /℃, flexural strength 162MPa, Young's modulus 83Gpa.

Example 5

According to the formula: MgO is 19wt%, Al ₂ O ₃ is 26wt%, SiO ₂ is 47wt%, ZrO ₂ is 2wt%, B ₂ O ₃ is 5wt%, K ₂ O is 1wt%, and the weight of the corresponding raw materials is accurately calculated , after accurate weighing, ball mill for 4 hours to make it evenly mixed; after drying, the mixture is placed in a crucible and melted, heated to 1450 ° C for 2 hours, and water quenched after melting is complete; then the obtained glass slag is subjected to wet ball milling , dried to obtain glass powder, ball-milled with deionized water for 8 hours, and dried to obtain a uniformly dispersed powder; after granulation and dry pressing, the powder was sintered at 950 ° C and kept for 1 hour to obtain low Thermally expanded cordierite-based glass-ceramic material.

In the low thermal expansion cordierite-based glass-ceramic material prepared in this example, the content of Mg ₂ Al ₄ Si ₅ O ₁₈ phase is 76.5%, and the content of (MgAl ₂ Si ₃ O ₁₀ ) _0.6 phase is 18.3%. The performance indicators are: dielectric constant 5.77 (@1MHz), dielectric loss 0.88×10 ^-3 (@1MHz), thermal expansion coefficient 2.58×10 ^-6 /℃, flexural strength 153MPa, Young's modulus 81Gpa.

The above descriptions are only specific embodiments of the present invention, and any feature disclosed in this specification, unless otherwise stated, may be replaced by other equivalent or alternative features with similar purposes; all the disclosed features, or All steps in a method or process, except mutually exclusive features and/or steps, may be combined in any way.

Claims (2)

1. A low-thermal expansion cordierite-based microcrystalline glass material is characterized by comprising the following components:

MgO：15～19wt％；

Al₂O₃：26～30wt％；

SiO₂：46～50wt％；

ZrO₂：2～6wt％；

B₂O₃：1～5wt％；

K₂O：1～3wt％；

the low thermal expansion cordierite-based microcrystalline glass material comprises: mg (magnesium)₂Al₄Si₅O₁₈And (MgAl)₂Si₃O₁₀)_0.6Phase of which Mg₂Al₄Si₅O₁₈The content of phase (MgAl) is 65.2-76.5%₂Si₃O₁₀)_0.6The content of the phase is 18.3-25.7%;

the low thermal expansion cordierite-based microcrystalline glass material has a thermal expansion coefficient of 2.5-3.5 x 10^-6/℃。

2. The method for producing a low thermal expansion cordierite-based microcrystalline glass material as defined in claim 1, comprising the steps of:

step 1: with MgO, Al₂O₃、SiO₂、ZrO₂、B₂O₃、K₂O is a component design formula, the actual dosage of the raw materials corresponding to each oxide is calculated according to the proportion, and the raw materials are uniformly mixed;

step 2: ball-milling for 2-4 hours, drying, placing the mixture in a crucible, melting at 1400-1450 ℃ for 1-2 hours, and pouring into deionized water to obtain transparent glass slag;

and 3, step 3: ball-milling the obtained glass slag in a ceramic pot for 1-1.5 hours, and drying to obtain glass powder;

and 4, step 4: ball-milling the obtained glass powder in a nylon tank for 6-8 hours, and drying to obtain uniformly dispersed powder;

and 5: and adding acrylic acid into the powder for granulation, performing dry pressing molding, sintering at 900-950 ℃, and preserving heat for 1-2 hours to obtain the low-thermal-expansion cordierite-based microcrystalline glass.

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