Multilayer glass ceramic dielectric material, sintered body, method for manufacturing a sintered body, and high-frequency circuit component

Abstract

The present invention provides: a multilayer glass ceramic dielectric material which has low dielectric characteristics and high mechanical strength in a high frequency range of 20 GHz or more; a sintered body; and a circuit member for high frequency use. A multilayer glass ceramic dielectric material according to the present invention is characterized by having a multilayer structure wherein at least an outer layer, an inner layer and another outer layer are sequentially stacked, and is also characterized in that: the outer layers are formed of a material which has a relative dielectric constant of 5.5 or less at a measurement temperature of 25°C at a frequency of 28 GHz after being sintered; and the inner layer is formed of a material, the thermal expansion coefficient of which after sintering is higher than the thermal expansion coefficient of the outer layers after sintering.

Description

Technical Field

[0005]

[0001] The present invention relates to a laminated glass ceramic dielectric material, a sintered body, and a high-frequency circuit member having a low dielectric constant and high mechanical strength, which are advantageous for signal processing in a high-frequency region of 20 GHz or higher.

Background Art

[0002] Alumina ceramics are widely used as wiring boards and circuit components. Alumina ceramics have a drawback that the signal processing speed is slow because the relative dielectric constant is as high as 10. Further, since tungsten having a high melting point must be used as the conductor material, there is also a drawback that the conductor loss increases.

[0003] In order to compensate for those drawbacks, a glass ceramic dielectric material composed of glass powder and ceramic powder has been developed, and a sintered body thereof is used as a dielectric layer. For example, a sintered body of a glass ceramic dielectric material using glass powder made of alkali borosilicate glass has a relative dielectric constant of 6 to 8, which is lower than that of an alumina ceramic material. Further, since it can be fired at a temperature of 1000° C. or lower, it has an advantage that it can be co-fired with a low-melting-point metal material such as Ag or Cu having low conductor loss, and these can be used as an inner layer conductor (see Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

[0005] ​​​​​​Incidentally, in recent years, the frequency bands used in mobile communication devices such as 5G and local network communication fields such as Wi-Fi have been increasing to over 20 GHz, and in such high-frequency ranges, there is a strong demand for further reduction of the dielectric constant of glass ceramic dielectric materials.

[0006] The transmission loss of electromagnetic waves in electronic circuits is proportional to the product of the square root of the dielectric constant of the circuit board, the dielectric loss tangent, and the frequency of the electromagnetic wave. The glass-ceramic dielectric materials disclosed in Patent Documents 1 and 2 have the problem of high transmission loss because the relative permittivity of the sintered body is not sufficiently low compared to the required value of 6 to 8. In addition, sintered bodies of glass-ceramic dielectric materials with low dielectric constants have low mechanical strength, which can lead to problems such as cracking and fissures during the process of mounting elements on a substrate.

[0007] To overcome the above challenges, it has been proposed to combine a low dielectric constant layer with a high-strength layer to achieve both reduced transmission loss and increased substrate strength (see Patent Document 3).

[0008] However, the dielectric material disclosed in Patent Document 3 had the problem of not having sufficient strength.

[0009] The object of the present invention is to provide a multilayer glass ceramic dielectric material, a sintered body, and a high-frequency circuit component having low dielectric properties and high mechanical strength in the high-frequency range of 20 GHz or higher. [Means for solving the problem]

[0010] The laminated glass ceramic dielectric material of the present invention has a laminated structure in which at least an outer layer, an inner layer, and another outer layer are stacked in that order, wherein the outer layer is made of a material whose relative permittivity at a measurement temperature of 25°C and a frequency of 28GHz after sintering is 5.5 or less, and the inner layer is made of a material whose coefficient of thermal expansion after sintering is higher than the coefficient of thermal expansion of the outer layer after sintering.

[0011] Here, the "relative permittivity at a measurement temperature of 25°C and a frequency of 28GHz" is measured using a sintered body densely sintered at 900°C as the measurement sample. The "thermal expansion coefficient" is the average value measured over a temperature range of 30 to 380°C using a sintered body densely sintered at 900°C as the measurement sample. The "inner layer" and "outer layer" are made of different materials. Furthermore, the "inner layer" and "outer layer" are not limited to being single layers each, but may be multiple layers made of substantially the same material stacked on top of each other. Substantially the same materials refer to materials whose difference in thermal expansion coefficient after firing is 1 ppm / K or less. Also, stacks of substantially the same materials become integrated into a single layer after sintering. In this case, the "thermal expansion coefficient" refers to the thermal expansion coefficient of a sintered body made of stacks of substantially the same materials densely sintered at 900°C. Furthermore, from the viewpoint of accurately enjoying the effects of the present invention, it is preferable that there be no other layers besides the "inner layer" and the "outer layer". However, the present invention does not completely exclude the possibility of further providing a different layer inside the outer layer.

[0012] Furthermore, in the laminated glass ceramic dielectric material of the present invention, the relative permittivity of the outer layer after firing at a measurement temperature of 25°C and a frequency of 28GHz is 5.5 or less. This ensures low dielectric properties of the sintered body.

[0013] Furthermore, in the laminated glass ceramic dielectric material of the present invention, the inner layer is made of a material whose thermal expansion coefficient after sintering is higher than that of the outer layer after sintering. This makes it possible to make the thermal shrinkage of the inner layer during firing greater than that of the outer layer. As a result, compressive stress is more likely to occur near the surface of both the front and back surfaces of the sintered body, thereby increasing the mechanical strength of the sintered body. The compressive stress value is approximately 50 to 100 MPa.

[0014] In the laminated glass ceramic dielectric material of the present invention, it is preferable that the inner layer is made of a material whose thermal expansion coefficient after sintering is 1.5 ppm / K or higher than that of the outer layer after sintering.

[0015] Furthermore, in the laminated glass ceramic dielectric material of the present invention, it is preferable that the inner layer contains at least crystalline glass powder.

[0016] On the other hand, in the laminated glass ceramic dielectric material of the present invention, it is preferable that the outer layer contains at least amorphous glass powder.

[0017] Here, "crystalline glass powder" refers to glass powder that precipitates crystals when fired at 900°C, and "amorphous glass powder" refers to glass powder that does not precipitate crystals when fired at 900°C. In the laminated glass ceramic dielectric material of the present invention, the inner layer contains at least crystalline glass powder and the outer layer contains at least amorphous glass powder, thereby increasing mechanical strength and making it easier to fire at temperatures below 1000°C, so that low-melting-point metal materials such as Ag and Cu can be used as the inner layer conductor.

[0018] The laminated glass ceramic dielectric material of the present invention is preferably used in the form of a laminated green sheet.

[0019] Furthermore, the sintered body of the present invention is a sintered body obtained by sintering the above-mentioned multilayer glass ceramic dielectric material, and it is preferable that one or more crystals selected from anorthite, sr feldspar, celsian, diopside, and willemite precipitate from the glass matrix of the inner layer. By restricting the crystal species that precipitate in the crystalline glass contained in the inner layer as described above, the mechanical strength of the sintered body can be increased.

[0020] In the sintered body of the present invention, it is preferable that the relative permittivity of the outer layer is 4 or less at a measurement temperature of 25°C and a frequency of 28 GHz. By lowering the relative permittivity of the outer layer as described above, signal processing can be performed in the outer layer.

[0021] Furthermore, in the sintered body of the present invention, it is preferable that the outer layer is substantially free of ceramic powder (the ceramic powder content in the outer layer is less than 0.5% by mass).

[0022] The sintered body of the present invention is a sintered body laminated and integrated in the order of at least an outer layer, an inner layer, and an outer layer, wherein the relative permittivity of the outer layer at a measurement temperature of 25 °C and a frequency of 28 GHz is 5.5 or less, and it is preferable that the coefficient of thermal expansion of the inner layer is higher than that of the outer layer.

[0023] In the method for manufacturing the sintered body of the present invention, it is preferable to fire the above-mentioned laminated glass ceramic dielectric material.

[0024] In the method for manufacturing the sintered body of the present invention, it is preferable to fire the above-mentioned laminated glass ceramic dielectric material at a temperature of 1000 °C or lower.

[0025] The high-frequency circuit member of the present invention is a high-frequency circuit member having a dielectric layer, and it is preferable that the dielectric layer is the above-mentioned sintered body.

Effects of the Invention

[0026] The laminated glass ceramic dielectric material of the present invention has a low dielectric property in the high-frequency region of 20 GHz or higher, and the sintered body has high mechanical strength. Therefore, the laminated glass ceramic dielectric material of the present invention is suitable as a high-frequency circuit member for 5G communication and the like.

Modes for Carrying Out the Invention

[0027] In this specification, the numerical range indicated by using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. The laminated glass ceramic dielectric material of the present invention is a laminate laminated in the order of an outer layer, an inner layer, and an outer layer, and particularly preferably a laminate in which the inner layer contains crystalline glass powder and the outer layer contains amorphous glass powder.

[0028] First, the inner layer will be described.

[0029] The glass powder constituting the inner layer preferably includes crystalline glass powder that exhibits a higher coefficient of thermal expansion than the outer layer after firing. For example, it is preferable to use crystalline glass powder that has the property of precipitating one or more crystals selected from anorthite, sr feldspar, celsian, diopside, and willemite after firing. Glass ceramics that precipitate the above crystals tend to have a high coefficient of thermal expansion and high mechanical strength, making it easier to increase the mechanical strength of the sintered body. The coefficient of thermal expansion of the inner layer glass ceramic after firing is, for example, about 6 to 11 ppm / K at 30 to 380°C.

[0030] To further increase the mechanical strength of the sintered body, it is preferable to include high-strength ceramic powder such as alumina or zirconia in the crystalline glass powder. When mixing in high-strength ceramic powder, it is preferable that the crystalline glass powder content be 50-80% by mass and the high-strength ceramic powder content be 20-50% by mass, and more preferably that the crystalline glass powder content be 60-75% by mass and the high-strength ceramic powder content be 25-40% by mass. If the high-strength ceramic powder content is too high, it becomes difficult to densify the sintered body. On the other hand, if the high-strength ceramic powder content is too low, the mechanical strength of the sintered body tends to decrease.

[0031] In addition to alumina and zirconia, other ceramic powders may be introduced as high-strength ceramic powders. For example, one or more types selected from silicon carbide, silicon nitride, and aluminum nitride can be used as other ceramic powders.

[0032] The crystallization temperature T1 of the inner layer is preferably 850-900°C, and particularly preferably 870-900°C. If T1 is too low, the substrate is prone to warping. On the other hand, if T1 is too high, the firing temperature will be too high.

[0033] The composition of the crystalline glass powder should be selected according to the crystal species to be precipitated. For crystalline glass powder from which anorthite precipitates, it is preferable that the glass composition contains, by mass%, SiO2 40-60%, Al2O3 1-20%, CaO 15-30%, and B2O 30-10%. For crystalline glass powder from which Sr-based feldspar precipitates, it is preferable that the glass composition contains, by mass%, SiO2 20-40%, Al2O3 20-40%, SrO 10-30%, MgO 10-20%, and B2O 30-10%. For crystalline glass powder from which celsian precipitates, it is preferable that the glass composition contains, by mass%, SiO2 35-60%, Al2O3 1-10%, BaO 20-40%, and MgO 10-20%. The crystalline glass powder from which diopside precipitates preferably contains, by mass%, SiO2 40-60%, Al2O 30-10%, MgO 10-25%, and CaO 15-35% as a glass composition. The crystalline glass powder from which willemite precipitates preferably contains, by mass%, SiO2 30-60%, CaO 10-30%, MgO 10-20%, and ZnO 10-30% as a glass composition.

[0034] The inner layer, after firing, preferably has a relative permittivity of 10 or less, particularly 9.5 or less, at 25°C and 28GHz. If the relative permittivity is too high, the signal processing speed tends to slow down. The lower limit of the relative permittivity is not particularly limited, but in practice it is 5 or higher.

[0035] Furthermore, after firing, the dielectric loss tangent of the inner layer is preferably 0.0040 or less, and particularly preferably 0.0038 or less, at 25°C and 28GHz. If the dielectric loss tangent is too high, the loss of the transmitted signal tends to increase. The lower limit of the dielectric loss tangent is not particularly limited, but in reality it is 0.0005 or higher.

[0036] Next, I will explain the outer layer.

[0037] The amorphous glass powder contained in the outer layer preferably exhibits a lower coefficient of thermal expansion than the inner layer after firing, and has a relative permittivity of 5.5 or less, particularly 4 or less, at 25°C and 28GHz. Furthermore, the dielectric loss tangent is preferably 0.0020 or less. Note that the coefficient of thermal expansion after firing is approximately 5.5 to 6.5 ppm / K when the outer layer is amorphous glass ceramic, and approximately 3.5 to 4.5 ppm / K when it is amorphous glass.

[0038] The amorphous glass powder is preferably a borosilicate glass with low expansion and low dielectric constant, and more preferably contains, by mass%, 70-80% SiO2, 15-30% B2O3, and 0.1-5% Li2O+Na2O+K2O (total amount of Li2O, Na2O, and K2O). Furthermore, the content of Li2O, Na2O, and K2O is preferably 0-3% each.

[0039] To further lower the dielectric constant, low-dielectric-constant ceramic powder with a dielectric constant of 5.5 or less, particularly 4 or less, may be added to the amorphous glass powder. If the dielectric constant of the amorphous glass powder is sufficiently low, the low-dielectric-constant ceramic powder may not be included. When low-dielectric-constant ceramic powder is included, it is preferable that the amorphous glass powder content is 60-80% by mass and the low-dielectric-constant ceramic powder content is 20-40% by mass. If the low-dielectric-constant ceramic powder content is too high, densification of the sintered body becomes difficult. On the other hand, if the low-dielectric-constant ceramic powder content is too low, the dielectric constant does not decrease easily.

[0040] The low dielectric constant ceramic powder is preferably α-quartz, α-cristobalite, or β-tridymite, having a relative permittivity of 5 or less and a dielectric loss tangent of 0.0010 or less in the high-frequency region of 20 GHz or higher.

[0041] The softening point T2 of the outer layer is preferably 770-840°C, particularly 790-830°C. If T2 is too low, the heat resistance will decrease. On the other hand, if T2 is too high, the firing temperature will be too high.

[0042] The outer layer, after firing, preferably has a relative permittivity of 5.5 or less, particularly 4 or less, at 25°C and 28GHz. If the relative permittivity is too high, the signal processing speed tends to slow down. The lower limit of the relative permittivity is not particularly limited, but in practice it is 2.5 or higher.

[0043] Furthermore, after firing, the dielectric loss tangent of the outer layer is preferably 0.0025 or less, and particularly preferably 0.0020 or less, at 25°C and 28GHz. If the dielectric loss tangent is too high, the loss of the transmitted signal tends to increase. The lower limit of the dielectric loss tangent is not particularly limited, but in reality it is 0.0005 or higher.

[0044] Next, the method for manufacturing the sintered body of the present invention is described below.

[0045] First, a slurry is prepared by adding a predetermined amount of binder, plasticizer, and solvent to the above-mentioned glass powder, or a mixed powder of glass powder and ceramic powder. Suitable binders include, for example, polyvinyl butyral resin and methacrylic acid resin; suitable plasticizers include, for example, dibutyl phthalate; and suitable solvents include, for example, toluene and methyl ethyl ketone.

[0046] Next, the slurry is formed into a green sheet using the doctor blade method, dried, cut to predetermined dimensions, and then mechanically processed to form via holes. For example, a low-resistance metal material that will serve as a silver conductor or electrode is printed on the via holes and the surface of the green sheet. Then, a sheet containing crystalline glass powder is placed as the inner layer and a sheet containing amorphous glass powder is placed as the outer layer, and these are laminated and integrated by thermocompression to obtain a laminated green sheet. It is preferable that the inner layer accounts for 1 / 3 or more of the total thickness of the laminated green sheet, and especially more than half. Specifically, the inner layer is preferably 0.2 to 3 mm thick after lamination, and the outer layers are preferably 0.1 to 1.5 mm thick. If the inner layer is too thin, it is difficult to obtain the effect of strength improvement due to the difference in thermal expansion coefficients between the inner and outer layers.

[0047] The temperature difference T1-T2 between the crystallization temperature T1 of the inner layer and the softening point T2 of the outer layer is preferably 50-120°C, and particularly preferably 60-110°C. If T1-T2 is too small, the substrate is prone to warping. On the other hand, if T1-T2 is too large, there is a risk of increased conductor diffusion.

[0048] Furthermore, a sintered body can be obtained by firing the laminated green sheets. The sintered body thus produced has conductors or electrodes inside or on its surface. From the viewpoint of using low-melting-point metal materials such as Ag and Cu, which have low conductor loss, the firing temperature is preferably 1000°C or lower, and especially 800-950°C.

[0049] Alternatively, a constraining layer made of alumina or similar material that does not shrink below 1000°C can be placed on both outer surfaces of the compressed body before firing, and a firing method that prevents shrinkage in the XY direction can be employed. By performing constraining firing, warping, cracking, and delamination between layers can be prevented.

[0050] In the fabricated sintered body, it is preferable that the thermal expansion coefficient of the inner layer is higher than that of the outer layer. Specifically, the difference between the thermal expansion coefficient of the inner layer and the outer layer is preferably 1.5 ppm / K or more, 1.6 ppm / K or more, particularly 1.7 ppm / K or more, and preferably 10 ppm / K or less, 6 ppm / K or less, particularly 5.3 ppm / K or less. The larger the difference in thermal expansion coefficients, the easier it is for compressive stress to occur near the surface of both the front and back surfaces of the sintered body, thereby increasing the mechanical strength of the sintered body. On the other hand, if the difference in thermal expansion coefficients is too large, delamination is more likely to occur at the interface between the inner and outer layers.

[0051] The three-point bending strength of the fabricated sintered body is preferably 300 MPa or higher, and more preferably 310 MPa or higher. The higher the three-point bending strength, the less likely cracks and other defects are to occur in the sintered body.

[0052] The high-frequency circuit member of the present invention is a high-frequency circuit member having a dielectric layer, wherein the dielectric layer is preferably the above-described sintered body. The high-frequency circuit component of the present invention can be manufactured by forming a coil with wiring or by connecting a Si-based or GaAs-based semiconductor chip to the surface of a sintered body manufactured as described above. [Examples]

[0053] The present invention will be described below based on examples. However, the present invention is not limited to the following examples, and the following examples are illustrative.

[0054] Table 1 shows examples of the present invention (samples No. 1 to 7) and comparative examples (sample No. 8). In Table 1, R2O refers to Li2O + Na2O + K2O. In Table 1, CTE refers to the coefficient of thermal expansion.

[0055] [Table 1]

[0056] Each sample was prepared as follows: First, glass raw materials of various oxides were mixed uniformly to achieve the glass composition shown in Table 1. The mixture was then placed in a platinum crucible and melted at 1400-1600°C for 3-8 hours. The molten glass was then formed into thin sheets using water-cooled rollers. Next, the resulting glass film was coarsely crushed, then wet-milled with alcohol using a ball mill, and classified to obtain glass powder with an average particle size of 1.5-3 μm.

[0057] Next, the above-mentioned glass powder was uniformly mixed with the amount of ceramic powder (average particle size 2 μm) shown in Table 1 to obtain a glass-ceramic dielectric material.

[0058] Next, a slurry was prepared by adding 15% by mass of polyvinyl butyral as a binder, 4% by mass of butyl benzyl phthalate as a plasticizer, and 30% by mass of toluene as a solvent to the obtained glass ceramic dielectric material. Then, the slurry was molded into a 150 μm green sheet using the doctor blade method, dried, cut to predetermined dimensions, and then laminated with four inner layers and two outer layers on the top and bottom, and integrated by thermocompression bonding. Furthermore, a sintered body was obtained by firing the resulting laminated green sheet at 900°C for 1 hour.

[0059] For each sample obtained in this manner, the crystalline phase was identified, and the relative permittivity, dielectric loss tangent, difference in thermal expansion coefficients between the inner and outer layers, three-point bending strength of the sintered body, and the difference between the crystallization temperature T1 of the inner layer and the softening point T2 of the outer layer were evaluated. The results are shown in Table 1.

[0060] The crystalline phase was identified by powder X-ray diffraction.

[0061] The relative permittivity and dielectric loss tangent were measured by molding a green sheet, sintering it at 900°C, processing it to a size of 25mm × 50mm × 0.1mm to create a measurement sample, and then measuring it at a temperature of 25°C and a frequency of 28GHz according to the measurement method for microwave dielectric properties of fine ceramic substrates (JIS R1641).

[0062] The difference in thermal expansion coefficients between the inner and outer layers (inner layer CTE - outer layer CTE) was calculated by measuring the inner and outer layers, which were separately sintered at 900°C within a temperature range of 30 to 380°C, using a thermomechanical analyzer.

[0063] The three-point bending strength was evaluated in accordance with JIS R1601.

[0064] The crystallization temperature T1 of the inner layer and the softening point T2 of the outer layer were measured using a macro-type differential thermal analyzer. Specifically, for the inner and outer layers before firing, measurements were taken using a macro-type differential thermal analyzer at a heating rate of 10°C / min up to 1050°C. In the resulting chart, the value of the fourth inflection point was defined as the softening point, and the strong exothermic peak as the crystallization temperature. The difference between the crystallization temperature and the softening point was calculated as T1-T2.

[0065] As is clear from the table, samples No. 1 to 7 had a difference in thermal expansion coefficient between the inner and outer layers (inner layer CTE - outer layer CTE) of 1.8 to 5.3 ppm / K, resulting in high three-point bending strengths of 200 to 380 MPa. In addition, the low relative permittivity of the outer layer (3.8 to 4.0) resulted in less signal attenuation at frequencies above 20 GHz.

[0066] On the other hand, sample No. 8 had a low three-point bending strength of 100 MPa because the difference in thermal expansion coefficients between the inner and outer layers (inner layer CTE - outer layer CTE) was -2.5 ppm / K.

Claims

1. A laminated glass ceramic dielectric material characterized by having a laminated structure in which at least an outer layer, an inner layer, and another outer layer are stacked in that order, wherein the outer layer is made of a material having a relative permittivity of 5.5 or less at a measurement temperature of 25°C and a frequency of 28 GHz after sintering, the outer layer contains at least amorphous glass powder, the amorphous glass powder contains, as a glass composition, 70-80% by mass of SiO2, 15-30% of B2O3, and 0.1-5% of Li2O + Na2O + K2O (total amount of Li2O, Na2O, and K2O), and the inner layer is made of a material whose coefficient of thermal expansion after sintering is higher than that of the outer layer after sintering.

2. The laminated glass ceramic dielectric material according to claim 1, characterized in that the inner layer is made of a material whose thermal expansion coefficient after sintering is 1.5 ppm / K or higher than the thermal expansion coefficient of the outer layer after firing.

3. The laminated glass ceramic dielectric material according to claim 1 or 2, characterized in that the inner layer contains at least crystalline glass powder.

4. A laminated glass ceramic dielectric material according to any one of claims 1 to 3, characterized in that it is used in the form of a laminated green sheet.

5. A sintered body obtained by sintering a multilayer glass ceramic dielectric material according to any one of claims 1 to 4, characterized in that one or more crystals selected from anorthite, sr feldspar, celsian, diopside, and willemite precipitate from the inner layer glass matrix.

6. The sintered body according to claim 5, characterized in that the relative permittivity of the outer layer is 4 or less at a measurement temperature of 25°C and a frequency of 28 GHz.

7. The sintered body according to claim 5 or 6, characterized in that the outer layer substantially does not contain ceramic powder.

8. A method for manufacturing a sintered body, characterized by firing a laminated glass ceramic dielectric material according to any one of claims 1 to 4.

9. The method for producing a sintered body according to claim 8, characterized by firing at a temperature of 1000°C or lower.

10. A high-frequency circuit member having a dielectric layer, characterized in that the dielectric layer is a sintered body according to any one of claims 5 to 7.

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