JP2022052429A - Glass ceramic dielectric material, sintered body and high frequency circuit member - Google Patents
Glass ceramic dielectric material, sintered body and high frequency circuit member Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 23
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021489 α-quartz Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000004020 conductor Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- -1 β-tridimite Chemical compound 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021493 α-cristobalite Inorganic materials 0.000 description 1
Classifications
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/16—Compositions for glass with special properties for dielectric glass
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
- H01B3/087—Chemical composition of glass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
Abstract
Description
本発明は、２０ＧＨｚ以上の高周波領域において、低い誘電率及び誘電正接、高い熱膨張係数を有するガラスセラミック誘電体材料、焼結体及び高周波用回路部材に関する。 The present invention relates to a glass-ceramic dielectric material having a low dielectric constant, a dielectric loss tangent, and a high thermal expansion coefficient in a high frequency region of 20 GHz or higher, a sintered body, and a circuit member for high frequency.
アルミナセラミックは、配線基板や回路部品として広く使用されている。アルミナセラミックは、比誘電率が１０と高いため、信号処理の速度が遅いという欠点がある。また、導体材料に高融点のタングステンを使用しなければならないため、導体損失が高くなるという欠点もある。 Alumina ceramics are widely used as wiring boards and circuit components. Alumina ceramic has a high relative permittivity of 10, so that it has a drawback that the signal processing speed is slow. In addition, since tungsten having a high melting point must be used as the conductor material, there is a drawback that the conductor loss becomes high.
その欠点を補うために、ガラス粉末とセラミック粉末からなるガラスセラミック誘電体材料が開発されており、その焼結体が誘電体層として使用されている。例えば、アルカリ硼珪酸ガラスからなるガラス粉末を用いたガラスセラミック誘電体材料は、比誘電率が６～８であり、アルミナセラミック材料のそれよりも低い。また１０００℃以下の温度で焼成し得るため、導体損失の低いＡｇ、Ｃｕ等の低融点の金属材料との同時焼成が可能であり、これらを内層導体として使用し得るという長所がある（特許文献１及び２参照）。 To make up for that shortcoming, a glass-ceramic dielectric material consisting of glass powder and ceramic powder has been developed, and the sintered body is used as a dielectric layer. For example, a glass-ceramic dielectric material using a glass powder made of alkaline borosilicate glass has a relative permittivity 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 can be simultaneously fired with a metal material having a low melting point such as Ag and Cu, which has a low conductor loss, and has an advantage that these can be used as an inner layer conductor (Patent Document). See 1 and 2).
ところで、近年、５Ｇに代表される移動体通信機器、ＷｉＦｉ等のローカルネットワーク通信分野において、利用される周波数帯域が２０ＧＨｚ以上と高くなってきており、高周波領域において、ガラスセラミック誘電体材料の更なる低誘電正接化が強く求められるようになってきている。 By the way, in recent years, in the field of local network communication such as mobile communication equipment typified by 5G and WiFi, the frequency band used has become as high as 20 GHz or more, and in the high frequency region, the glass ceramic dielectric material is further increased. There is a strong demand for low dielectric loss tangent.
電磁波の電子回路での伝送損失は、回路基板の誘電率の平方根、誘電正接、電磁波の周波数の積に比例する。上記特許文献で開示されているガラスセラミック誘電体材料は、高周波領域における誘電特性、特に誘電正接が十分に低くないため、伝送損失が大きくなるという問題があった。 The transmission loss of an electromagnetic wave in an electronic circuit is proportional to the product of the square root of the permittivity of the circuit board, the dielectric loss tangent, and the frequency of the electromagnetic wave. The glass-ceramic dielectric material disclosed in the above patent document has a problem that the dielectric property in a high frequency region, particularly the dielectric loss tangent is not sufficiently low, so that the transmission loss becomes large.
また、従来のガラスセラミック誘電体材料は、熱膨張係数が４～７ｐｐｍ／℃と低いため、樹脂のマザーボードに半田付けした後、ヒートサイクルをかけると、熱膨張差によって歪が生じ、断線や亀裂が生じるという不具合が発生することがあった。 Further, since the conventional glass-ceramic dielectric material has a low coefficient of thermal expansion of 4 to 7 ppm / ° C., when a heat cycle is applied after soldering to a resin motherboard, distortion occurs due to the difference in thermal expansion, resulting in disconnection or cracking. There was a problem that the problem occurred.
本発明の目的は、１０００℃以下の温度で焼成でき、しかも２０ＧＨｚ以上での高周波領域において、低い誘電特性と高い熱膨張係数を有するガラスセラミック誘電体材料、焼結体及び高周波用回路部材を提供することである。 An object of the present invention is to provide a glass-ceramic dielectric material, a sintered body, and a circuit member for high frequency, which can be fired at a temperature of 1000 ° C. or lower and have a low dielectric property and a high coefficient of thermal expansion in a high frequency region at 20 GHz or higher. It is to be.
本発明者は、種々の実験を重ねた結果、特定のガラス組成を有するガラス粉末とα石英粉末とを複合化することにより、上記技術的課題を解決し得ることを見出し、本発明として提案するものである。即ち、本発明のガラスセラミック誘電体材料は、ガラス粉末とα石英粉末を含有するガラスセラミック誘電体材料であって、ガラス粉末の含有量が６０～８０質量％、α石英粉末の含有量が２０～４０質量％であり、且つ、ガラス粉末が、ガラス組成として、質量％で、ＳｉＯ２ ３８～５０％、ＭｇＯ １０～２０％、ＣａＯ １５～２５％、ＺｎＯ １５～２５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０～２％未満を含有することを特徴とする。ここで、「Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ」は、Ｌｉ２Ｏ、Ｎａ２Ｏ及びＫ２Ｏの合量を指す。 As a result of repeating various experiments, the present inventor has found that the above technical problem can be solved by combining a glass powder having a specific glass composition and an α-quartz powder, and proposes the present invention. It is a thing. That is, the glass-ceramic dielectric material of the present invention is a glass-ceramic dielectric material containing glass powder and α-quartz powder, and the content of glass powder is 60 to 80% by mass and the content of α-quartz powder is 20. -40% by mass, and the glass powder has a glass composition of 238-50 %, MgO 10-20%, CaO 15-25%, ZnO 15-25%, Li 2O + Na 2 by mass%. It is characterized by containing O + K 2 O 0 to less than 2%. Here, "Li 2 O + Na 2 O + K 2 O" refers to the total amount of Li 2 O, Na 2 O and K 2 O.
本発明の焼結体は、上記のガラスセラミック誘電体材料を焼結させた焼結体であって、熱膨張係数が９～１１ｐｐｍ／℃であり、２８ＧＨｚでの比誘電率が５．５～５．９であり、且つ、２８ＧＨｚでの誘電正接が０．００１０～０．００２０であることが好ましい。ここで、「熱膨張係数」は、３０～３８０℃の温度範囲において、熱機械分析装置にて測定した値を指す。「比誘電率」と「誘電正接」は、ファインセラミックス基板のマイクロ波誘電特性の測定方法（ＪＩＳ Ｒ１６４１）に基づいて、測定温度２５℃、周波数２８ＧＨｚで測定した値を指す。 The sintered body of the present invention is a sintered body obtained by sintering the above-mentioned glass-ceramic dielectric material, has a thermal expansion coefficient of 9 to 11 ppm / ° C., and has a relative permittivity of 5.5 to 28 GHz. It is preferably 5.9 and the dielectric loss tangent at 28 GHz is preferably 0.0010 to 0.0020. Here, the "coefficient of thermal expansion" refers to a value measured by a thermomechanical analyzer in a temperature range of 30 to 380 ° C. “Relative permittivity” and “dielectric loss tangent” refer to values measured at a measurement temperature of 25 ° C. and a frequency of 28 GHz based on a method for measuring microwave dielectric properties of a fine ceramic substrate (JIS R1641).
本発明の高周波回路部材は、誘電体層を有する高周波用回路部材であって、誘電体層が上記の焼結体であることが好ましい。 The high-frequency circuit member of the present invention is a high-frequency circuit member having a dielectric layer, and the dielectric layer is preferably the above-mentioned sintered body.
本発明のガラスセラミック誘電体材料は、１０００℃以下の低温で焼成可能であり、Ａｇ、Ｃｕ等の低融点の金属材料を内層導体として使用することができる。しかも２０ＧＨｚ以上の高周波領域において低い誘電特性を有し、熱膨張係数が９～１０ｐｐｍ／℃と高い。よって、本発明のガラスセラミック誘電体材料は、樹脂製マザーボードに実装する高周波用回路部材として好適である。 The glass-ceramic dielectric material of the present invention can be fired at a low temperature of 1000 ° C. or lower, and a metal material having a low melting point such as Ag or Cu can be used as the inner layer conductor. Moreover, it has a low dielectric property in a high frequency region of 20 GHz or higher, and has a high coefficient of thermal expansion of 9 to 10 ppm / ° C. Therefore, the glass-ceramic dielectric material of the present invention is suitable as a high-frequency circuit member to be mounted on a resin motherboard.
本発明のガラスセラミック誘電体材料において、ガラス粉末の含有量が６０～８０質量％、α石英粉末の含有量が２０～４０質量％であり、ガラス粉末の含有量が６５～７５質量％、α石英粉末の含有量が２５～３５質量％が好ましい。α石英粉末が多くなると、焼成体の緻密化が困難になり、α石英粉末が少なくなると、焼成体の曲げ強度が低下し易くなる。 In the glass-ceramic dielectric material of the present invention, the content of glass powder is 60 to 80% by mass, the content of α-quartz powder is 20 to 40% by mass, the content of glass powder is 65 to 75% by mass, and α. The content of the quartz powder is preferably 25 to 35% by mass. When the amount of α-quartz powder is large, it becomes difficult to densify the fired body, and when the amount of α-quartz powder is small, the bending strength of the fired body tends to decrease.
セラミック粉末として、α石英以外に他のセラミック粉末を導入してもよい。例えばαクリストバライト、βトリジマイト、ムライト、ジルコニア、コージエライトの一種又は二種以上を使用することができる。 As the ceramic powder, other ceramic powder may be introduced in addition to α-quartz. For example, one or more of α-cristobalite, β-tridimite, mullite, zirconia, and cordierite can be used.
本発明のガラスセラミック誘電体材料において、ガラス粉末は、ガラス組成として、質量％で、ＳｉＯ２ ３８～５０％、ＭｇＯ １０～２０％、ＣａＯ １５～２５％、ＺｎＯ １５～２５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０～２％未満を含有する。各成分の含有範囲を上記のように限定した理由を以下に述べる。 In the glass-ceramic dielectric material of the present invention, the glass powder has a glass composition of SiO 2 38 to 50%, MgO 10 to 20%, CaO 15 to 25%, ZnO 15 to 25%, Li 2 O + Na in terms of glass composition. 2 O + K 2 O Contains less than 0-2%. The reason for limiting the content range of each component as described above will be described below.
ＳｉＯ２は、ガラスのネットワークフォーマーとなる成分である。ＳｉＯ２の含有量が多くなると、焼成温度が高くなる傾向にあり、導体や電極としてＡｇやＣｕを使用できなくなる虞がある。一方、ＳｉＯ２の含有量が少なくなると、ガラス化が困難になる。また低誘電特性を得難くなる。よって、ＳｉＯ２の含有量は３８～５０％、特に４０～４８％が好ましい。 SiO 2 is a component that serves as a network former for glass. When the content of SiO 2 is large, the firing temperature tends to be high, and there is a risk that Ag or Cu cannot be used as a conductor or an electrode. On the other hand, when the content of SiO 2 is low, vitrification becomes difficult. In addition, it becomes difficult to obtain low dielectric properties. Therefore, the content of SiO 2 is preferably 38 to 50%, particularly preferably 40 to 48%.
ＭｇＯ、ＣａＯ、ＺｎＯは、何れもガラス粉末の軟化点を低下させる効果がある。それぞれ限定範囲から多い領域では、ガラス化が困難になり、限定範囲より少ない領域では、軟化点が高くなり過ぎる。また含有範囲を外れると、誘電正接が０．００２０以上になり易い。 MgO, CaO, and ZnO all have the effect of lowering the softening point of the glass powder. In each region from the limited range to a large amount, vitrification becomes difficult, and in a region less than the limited range, the softening point becomes too high. Further, if it is out of the content range, the dielectric loss tangent tends to be 0.0020 or more.
アルカリ金属酸化物（Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ）は、焼成温度を低下させる成分であるが、高周波領域での誘電正接を上昇させる成分である。よって、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏの含有量は２％未満であり、好ましくは１％未満、０．５％未満、特に０．１％未満である。なお、Ｌｉ２Ｏの含有量は、好ましくは０．５％未満、特に０．１％未満である。Ｎａ２Ｏの含有量は、好ましくは０．５％未満、特に０．１％未満である。Ｋ２Ｏの含有量は、好ましくは０．５％未満、特に０．１％未満である。 Alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are components that lower the firing temperature, but increase the dielectric loss tangent in the high frequency region. Therefore, the content of Li 2 O + Na 2 O + K 2 O is less than 2%, preferably less than 1%, less than 0.5%, particularly less than 0.1%. The content of Li 2 O is preferably less than 0.5%, particularly less than 0.1%. The content of Na 2 O is preferably less than 0.5%, particularly less than 0.1%. The content of K2O is preferably less than 0.5%, particularly less than 0.1%.
上記成分以外にも、誘電特性を損なわない範囲でＢ２Ｏ３、Ａｌ２Ｏ３等の成分をそれぞれ３％まで添加してもよい。 In addition to the above components, components such as B 2 O 3 and Al 2 O 3 may be added up to 3% each as long as the dielectric properties are not impaired.
本発明の焼結体は、上記のガラスセラミック誘電体材料を焼結させた焼結体である。本発明の焼結体において、焼結体の熱膨張係数は９～１１ｐｐｍ／℃が好ましい。焼結体の熱膨張係数が低過ぎると、樹脂のマザーボードに半田付けした後、ヒートサイクルをかける場合に、熱膨張差によって歪が生じ易くなる。 The sintered body of the present invention is a sintered body obtained by sintering the above-mentioned glass-ceramic dielectric material. In the sintered body of the present invention, the coefficient of thermal expansion of the sintered body is preferably 9 to 11 ppm / ° C. If the coefficient of thermal expansion of the sintered body is too low, distortion is likely to occur due to the difference in thermal expansion when a heat cycle is applied after soldering to the resin motherboard.
本発明の焼結体において、２８ＧＨｚでの比誘電率は５．５～５．９が好ましく、２８ＧＨｚでの誘電正接は０．００１０～０．００２０が好ましい。比誘電率や誘電正接が高くなると、伝送信号の損失が大きくなり易く、また信号処理の速度が遅くなり易い。 In the sintered body of the present invention, the relative permittivity at 28 GHz is preferably 5.5 to 5.9, and the dielectric loss tangent at 28 GHz is preferably 0.0010 to 0.0020. When the relative permittivity and the dielectric loss tangent are high, the loss of the transmission signal tends to be large, and the speed of signal processing tends to be slow.
次に本発明の焼結体の製造方法を以下に述べる。 Next, the method for producing the sintered body of the present invention will be described below.
まず、上記のガラス粉末とα石英粉末の混合粉末に、所定量の結合剤、可塑剤及び溶剤を添加してスラリーを調製する。結合剤としては例えばポリビニルブチラール樹脂、メタアクリル酸樹脂等、可塑剤としては例えばフタル酸ジブチル等、溶剤としては例えばトルエン、メチルエチルケトン等が好適である。 First, a predetermined amount of a binder, a plasticizer and a solvent are added to the mixed powder of the above glass powder and α-quartz powder to prepare a slurry. As the binder, for example, polyvinyl butyral resin, methacrylic acid resin and the like, as the plasticizer, for example, dibutyl phthalate and the like, and as the solvent, for example, toluene, methyl ethyl ketone and the like are suitable.
次いで上記のスラリーを、ドクターブレード法によってグリーンシートに成型した後、乾燥させ、所定寸法に切断してから、機械的加工を施してバイアホールを形成し、例えば、銀導体や電極となる低抵抗金属材料をバイアホール及びグリーンシート表面に印刷する。次いでこのようなグリーンシートを複数枚積層し、熱圧着によって一体化する。 Next, the above slurry is molded into a green sheet by the doctor blade method, dried, cut to a predetermined size, and then mechanically processed to form a via hole, for example, a low resistance to be a silver conductor or an electrode. The metallic material is printed on the via holes and the surface of the green sheet. Next, a plurality of such green sheets are laminated and integrated by thermocompression bonding.
更に、積層グリーンシートを焼成すると焼結体を得ることができる。このようにして作製された焼結体は、内部や表面に導体や電極を備えている。なお、導体損失の低いＡｇ、Ｃｕ等の低融点の金属材料を使用する観点から、焼成温度は１０００℃以下、特に８００～９５０℃の温度であることが望ましい。 Further, a sintered body can be obtained by firing the laminated green sheet. The sintered body thus produced has conductors and electrodes inside and on the surface. From the viewpoint of using a metal material having a low melting point such as Ag and Cu having a low conductor loss, the firing temperature is preferably 1000 ° C. or lower, particularly 800 to 950 ° C.
焼結体の製造方法として、グリーンシートを用いる例を挙げたが、本発明はこれに限定されるものではなく、バインダーを含む顆粒を作製して、プレス成型を行う等の各種方法を適用することができる。 An example of using a green sheet has been given as a method for producing a sintered body, but the present invention is not limited to this, and various methods such as producing granules containing a binder and performing press molding are applied. be able to.
本発明の高周波用回路部材は、配線でコイルを形成したり、上記のようにして作製した焼結体表面上にＳｉ系やＧａＡｓ系の半導体素子のチップを接続したりすることで作製することができる。 The circuit member for high frequency of the present invention is manufactured by forming a coil by wiring or connecting a chip of a Si-based or GaAs-based semiconductor element on the surface of the sintered body manufactured as described above. Can be done.
以下、実施例に基づいて本発明を説明する。但し、本発明は以下の実施例に限定されず、以下の実施例は例示である。 Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples, and the following examples are examples.
表１は、本発明の実施例（試料Ｎｏ．１～４）と比較例（試料Ｎｏ．５、６）を示している。なお、表中のＲ２Ｏは、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏを指す。 Table 1 shows Examples (Samples Nos. 1 to 4) and Comparative Examples (Samples Nos. 5 and 6) of the present invention. In addition, R 2 O in the table refers to Li 2 O + Na 2 O + K 2 O.
各試料は、次のようにして作製した。まず、表中に示すガラス組成となるように、各種酸化物のガラス原料を調合し、均一に混合した後、白金坩堝に入れて１４００～１５００℃で３～８時間溶融し、水冷ローラーによって溶融ガラスを薄板状に成形した。次いで、得られたガラスフィルムを粗砕した後、アルコールを加えてボールミルにより湿式粉砕し、平均粒径が１．５～３μｍとなるように分級してガラス粉末を得た。 Each sample was prepared as follows. First, glass raw materials of various oxides are mixed so as to have the glass composition shown in the table, mixed uniformly, then placed in a platinum crucible and melted at 1400 to 1500 ° C. for 3 to 8 hours, and melted by a water-cooled roller. The glass was formed into a thin plate. Next, the obtained glass film was roughly crushed, alcohol was added, and wet pulverized by a ball mill, and the mixture was classified so that the average particle size was 1.5 to 3 μm to obtain a glass powder.
次に、上記のガラス粉末に、表中に示す量のセラミック粉末（平均粒径２μｍ）を均一に混合して、ガラスセラミック誘電体材料を得た。 Next, the ceramic powder (average particle size 2 μm) shown in the table was uniformly mixed with the above glass powder to obtain a glass-ceramic dielectric material.
続いて、得られたガラスセラミック誘電体材料に、結合剤としてポリビニルブチラールを１５質量％、可塑剤としてブチルベンジルフタレートを４質量％、及び溶剤としてトルエンを３０質量％添加してスラリーを調整した。次いで、上記のスラリーをドクターブレード法によってグリーンシートに成型し、乾燥させ、所定寸法に切断した後、複数枚を積層し、熱圧着によって一体化した。更に、得られた積層グリーンシートを焼成することによって焼結体を得た。 Subsequently, 15% by mass of polyvinyl butyral as a binder, 4% by mass of butylbenzyl phthalate as a plasticizer, and 30% by mass of toluene as a solvent were added to the obtained glass-ceramic dielectric material to prepare a slurry. Next, the above slurry was molded into a green sheet by the doctor blade method, dried, cut to a predetermined size, and then a plurality of sheets were laminated and integrated by thermocompression bonding. Further, the obtained laminated green sheet was fired to obtain a sintered body.
このようにして得られた各試料について、焼成温度、誘電特性及び熱膨張係数を評価した。その結果を表１に示す。 For each sample thus obtained, the firing temperature, the dielectric property and the coefficient of thermal expansion were evaluated. The results are shown in Table 1.
焼成温度は、種々の温度で焼成した焼結体にインクを塗布した後に拭き取り、インクが残らない（＝緻密に焼結した）最低の温度を表記したものである。 The firing temperature indicates the lowest temperature at which ink is applied to sintered bodies fired at various temperatures and then wiped off so that no ink remains (= finely sintered).
比誘電率と誘電正接は、グリーンシート成型したものを表中に示す焼成温度で焼結した後、２５ｍｍ×５０ｍｍ×０．１ｍｍの大きさに加工して、測定試料とした上で、ファインセラミックス基板のマイクロ波誘電特性の測定方法（ＪＩＳ Ｒ１６４１）に基づいて、測定温度２５℃、周波数２８ＧＨｚで測定したものである。 For the relative permittivity and dielectric tangent, after sintering the green sheet molded product at the firing temperature shown in the table, it is processed to a size of 25 mm x 50 mm x 0.1 mm to make a measurement sample, and then fine ceramics. It was measured at a measurement temperature of 25 ° C. and a frequency of 28 GHz based on a method for measuring microwave dielectric characteristics of a substrate (JIS R1641).
熱膨張係数は、３０～３８０℃の温度範囲において、熱機械分析装置にて測定したものである。 The coefficient of thermal expansion is measured by a thermomechanical analyzer in a temperature range of 30 to 380 ° C.
表から明らかなように、試料Ｎｏ．１～４は、周波数２８ＧＨｚでの比誘電率は５．５～５．９、周波数２８ＧＨｚでの誘電正接が０．００１２～０．００１９であり、高周波領域での誘電特性が低かった。また焼成温度が９３０℃以下と低く、熱膨張係数が９．２～１０．８ｐｐｍ／℃と高かった。 As is clear from the table, the sample No. In Nos. 1 to 4, the relative permittivity at a frequency of 28 GHz was 5.5 to 5.9, the dielectric loss tangent at a frequency of 28 GHz was 0.0012 to 0.0019, and the dielectric properties in the high frequency region were low. The firing temperature was as low as 930 ° C. or lower, and the coefficient of thermal expansion was as high as 9.2 to 10.8 ppm / ° C.
一方、試料Ｎｏ．５は、ガラス粉末中のアルカリ金属酸化物が多いため、周波数２８ＧＨｚでの誘電正接が０．００５５であり、高周波領域での誘電特性が高かった。試料Ｎｏ．６は、セラミック粉末がアルミナであるため、比誘電率が７．９と高く、熱膨張係数が８．５ｐｐｍ／℃と低かった。 On the other hand, sample No. In No. 5, since the amount of alkali metal oxide in the glass powder was large, the dielectric loss tangent at a frequency of 28 GHz was 0.0055, and the dielectric property in the high frequency region was high. Sample No. In No. 6, since the ceramic powder was alumina, the relative permittivity was as high as 7.9 and the coefficient of thermal expansion was as low as 8.5 ppm / ° C.
Claims (3)
ガラス粉末の含有量が６０～８０質量％、α石英粉末の含有量が２０～４０質量％であり、
且つ、ガラス粉末が、ガラス組成として、質量％で、ＳｉＯ２ ３８～５０％、ＭｇＯ １０～２０％、ＣａＯ １５～２５％、ＺｎＯ １５～２５％、Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ０～２％未満を含有することを特徴とするガラスセラミック誘電体材料。 A glass-ceramic dielectric material containing glass powder and α-quartz powder.
The content of the glass powder is 60 to 80% by mass, the content of the α-quartz powder is 20 to 40% by mass, and the content is 20 to 40% by mass.
Moreover, the glass powder has a glass composition of SiO 2 38 to 50%, MgO 10 to 20%, CaO 15 to 25%, ZnO 15 to 25%, Li 2 O + Na 2 O + K 2 O 0 to 2% in terms of glass composition. A glass-ceramic dielectric material characterized by containing less than.
熱膨張係数が９～１１ｐｐｍ／℃であり、
２８ＧＨｚでの比誘電率が５．５～５．９であり、
且つ、２８ＧＨｚでの誘電正接が０．００１０～０．００２０であることを特徴とする焼結体。 A sintered body obtained by sintering the glass-ceramic dielectric material according to claim 1.
The coefficient of thermal expansion is 9 to 11 ppm / ° C.
The relative permittivity at 28 GHz is 5.5 to 5.9.
Moreover, the sintered body is characterized in that the dielectric loss tangent at 28 GHz is 0.0010 to 0.0020.
誘電体層が請求項２に記載の焼結体であることを特徴する高周波回路部材。 A high-frequency circuit member having a dielectric layer,
A high-frequency circuit member characterized in that the dielectric layer is the sintered body according to claim 2.
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