JP4736342B2 - Glass ceramic raw material composition, glass ceramic sintered body and glass ceramic multilayer substrate - Google Patents
Glass ceramic raw material composition, glass ceramic sintered body and glass ceramic multilayer substrate Download PDFInfo
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- 239000002241 glass-ceramic Substances 0.000 title claims description 131
- 239000000758 substrate Substances 0.000 title claims description 63
- 239000000203 mixture Substances 0.000 title claims description 59
- 239000002994 raw material Substances 0.000 title claims description 38
- 239000000843 powder Substances 0.000 claims description 121
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 104
- 239000011521 glass Substances 0.000 claims description 91
- 239000000919 ceramic Substances 0.000 claims description 70
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 47
- 239000000395 magnesium oxide Substances 0.000 claims description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 44
- 239000013078 crystal Substances 0.000 claims description 44
- 239000004020 conductor Substances 0.000 claims description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 22
- 239000011787 zinc oxide Substances 0.000 claims description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052810 boron oxide Inorganic materials 0.000 claims description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 239000006112 glass ceramic composition Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010453 quartz Substances 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
- 239000006063 cullet Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910015999 BaAl Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- TZIBOXWEBBRIBM-UHFFFAOYSA-N cerium(3+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ce+3] TZIBOXWEBBRIBM-UHFFFAOYSA-N 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000003870 refractory metal Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 BaCO 3 Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Inorganic Insulating Materials (AREA)
Description
この発明は、ガラスセラミック原料組成物、ガラスセラミック焼結体およびガラスセラミック多層基板に関するもので、特に、１０００℃以下の低温焼成によって得られ、半導体デバイスやチップ型積層コンデンサなどの表面実装部品を搭載することが可能なガラスセラミック多層基板に関するものである。 TECHNICAL FIELD The present invention relates to a glass ceramic raw material composition, a glass ceramic sintered body, and a glass ceramic multilayer substrate, and is particularly obtained by low-temperature firing at 1000 ° C. or less and mounted with surface mount components such as semiconductor devices and chip type multilayer capacitors. The present invention relates to a glass ceramic multilayer substrate that can be used.
従来、半導体デバイスやチップ型積層コンデンサなどを搭載するための基板は、アルミナ基板が主流であった。アルミナ基板を得るためには、アルミナを主成分とするセラミックグリーンシートを約１６００℃という高温で焼成しなければならない。そのため、アルミナからなるセラミックグリーンシートをもって内部導体パターンを有するセラミック多層基板を構成する場合には、内部導体パターンの材料としてタングステンやモリブデン等の高融点金属を用いなければならない。ところが、これらの高融点金属は比抵抗が大きく、特に高周波領域においては、信号の伝送損失を増大させる要因として無視できない。 Conventionally, alumina substrates have been the mainstream for mounting semiconductor devices, chip type multilayer capacitors, and the like. In order to obtain an alumina substrate, a ceramic green sheet mainly composed of alumina must be fired at a high temperature of about 1600 ° C. For this reason, when a ceramic multilayer substrate having an internal conductor pattern is formed using a ceramic green sheet made of alumina, a refractory metal such as tungsten or molybdenum must be used as a material for the internal conductor pattern. However, these refractory metals have a large specific resistance, and cannot be ignored as a factor that increases signal transmission loss, particularly in the high frequency region.
そこで、たとえば、特開２００３−２０１１７０号公報（特許文献１）に示されているように、内部導体パターンの材料としてＡｇなどの低抵抗金属の使用を可能にするガラスセラミック多層基板が注目されている。
特開２００３−２０１１７０号公報に開示されたガラスセラミック多層基板は、ＳｉＯ2を３０〜６０モル％、ＢａＯを２０〜４０モル％、ＭｇＯを０〜４０モル％、ＺｎＯを０〜４０モル％、Ｂ2Ｏ3を０〜２０モル％含むガラス粉末と、Ａｌ2Ｏ3を主とするセラミック粉末とからなるガラスセラミック原料組成物を焼成することによって得られるものである。 JP 2003 2 01170 No. glass ceramic multilayer substrate which is disclosed in Japanese is a SiO 2 30 to 60 mol%, a BaO 20 to 40 mol%, the MgO 0 to 40 mol%, the ZnO 0 to 40 mol% It is obtained by firing a glass ceramic raw material composition comprising a glass powder containing 0 to 20 mol% of B 2 O 3 and a ceramic powder mainly containing Al 2 O 3 .
このガラスセラミック原料組成物は、１０００℃以下での焼成が可能であるため、比抵抗の小さなＡｇ系導体パターンと同時焼成することができ、さらに、得られたガラスセラミック多層基板は、ＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2を主とする結晶相を析出し得るものであって、測定周波数１０ＧＨｚでのＱ値が４００以上のように、高周波特性に優れた基板である。 Since this glass ceramic raw material composition can be fired at 1000 ° C. or less, it can be fired simultaneously with an Ag-based conductor pattern having a small specific resistance. Further, the obtained glass ceramic multilayer substrate is made of BaO · Al The substrate is capable of precipitating a crystal phase mainly composed of 2 O 3 .2SiO 2 , and has a high frequency characteristic such as a Q value of 400 or more at a measurement frequency of 10 GHz.
しかしながら、このガラスセラミック多層基板は、原料組成物であるガラス中のＳｉＯ2やＢａＯを、ＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2結晶相の構成成分として利用するものであるため、結晶相の析出量によってガラス相の組成が変動し、これに応じて、ガラスセラミック多層基板の特性も変動することがあった。 However, since this glass ceramic multilayer substrate uses SiO 2 and BaO in the glass as the raw material composition as a constituent component of the BaO · Al 2 O 3 · 2SiO 2 crystal phase, the amount of crystal phase deposited As a result, the composition of the glass phase fluctuated, and the characteristics of the glass ceramic multilayer substrate may fluctuate accordingly.
すなわち、本発明は、上述した実情に鑑みてなされたものであり、その目的は、特性の変動が少なく信頼性に優れ、さらに高周波帯域において優れた電気特性を有したガラスセラミック多層基板、ならびに、このガラスセラミック多層基板を形成する際に用いられるガラスセラミック原料組成物およびガラスセラミック焼結体を提供することにある。 That is, the present invention has been made in view of the above-described circumstances, and the purpose thereof is a glass ceramic multilayer substrate having excellent electrical characteristics in a high frequency band, with excellent reliability with little fluctuation in characteristics, and An object of the present invention is to provide a glass ceramic raw material composition and a glass ceramic sintered body used when forming the glass ceramic multilayer substrate.
すなわち、本発明は、酸化ケイ素をＳｉＯ2換算で２０〜４０重量％、酸化バリウムをＢａＯ換算で３０〜６０重量％、酸化マグネシウムをＭｇＯ換算で５〜２０重量％、酸化亜鉛をＺｎＯ換算で０〜１０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１０重量％、酸化ホウ素をＢ2Ｏ3換算で０〜１０重量％含有するガラス粉末を５０〜６５重量％と、酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末を３５〜５０重量％と、を含み、さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有するガラスセラミック原料組成物に係るものである。 Namely, the present invention is 20 to 40 wt% of silicon oxide in terms of SiO 2, 30-60 wt% barium oxide in terms of BaO, magnesium oxide 5-20 wt% in terms of MgO, an oxide of zinc calculated as ZnO 0 10 wt%, SiO 0-10 wt% of aluminum oxide in terms of Al 2 O 3, and 50-65 wt% of glass powder containing 0-10 wt% of boron oxide in terms of B 2 O 3, silicon oxide 50-70% by weight 2 equivalent, 10 to 40 wt% of barium oxide in terms of BaO, 0 to 20 wt% of magnesium oxide in terms of MgO, the ceramic containing 0-15 wt% of aluminum oxide in terms of Al 2 O 3 powder observed containing a 35-50% by weight, the a, further, in the case where at least one of cerium oxide titanium oxide, 5 wt% or less, respectively cerium oxide in terms of CeO 2, The titanium is intended according to the glass-ceramic raw material composition in a proportion of 5 wt% or less in terms of TiO 2.
また、本発明は、本発明のガラスセラミック原料組成物を焼成してなり、ＢａＯ・２ＭｇＯ・２ＳｉＯ2を主とする結晶相を析出しているガラスセラミック焼結体を提供するものである。 Further, the present invention is to provide a glass ceramic material composition becomes by firing the glass ceramic sintered body of BaO · 2MgO · 2SiO 2 are precipitated a crystal phase mainly of the present invention.
さらに、本発明は、本発明のガラスセラミック原料組成物を焼成してなり、ＢａＯ・２ＭｇＯ・２ＳｉＯ2を主とする結晶相を析出している複数のガラスセラミック絶縁層と、前記複数のガラスセラミック絶縁層の間に設けられるＡｇ系導体パターンと、を備えるガラスセラミック多層基板を提供するものである。 Furthermore, the present invention is made by firing a glass ceramic material composition of the present invention, a plurality of glass-ceramic insulating layer of BaO · 2MgO · 2SiO 2 are precipitated a crystal phase mainly, the plurality of glass ceramic A glass ceramic multilayer substrate comprising an Ag-based conductor pattern provided between insulating layers is provided.
本発明のガラスセラミック原料組成物は、酸化ケイ素をＳｉＯ2換算で２０〜４０重量％、酸化バリウムをＢａＯ換算で３０〜６０重量％、酸化マグネシウムをＭｇＯ換算で５〜２０重量％、酸化亜鉛をＺｎＯ換算で０〜１０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１０重量％、酸化ホウ素をＢ2Ｏ3換算で０〜１０重量％含有するガラス粉末を５０〜６５重量％と、酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末を３５〜５０重量％と、を含み、さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有するものであり、これを焼成した際に析出するＢａＯ・２ＭｇＯ・２ＳｉＯ2主結晶相の構成成分が、ガラスだけでなく、セラミック中にも含まれているので、ガラス相の組成が変動しにくく、安定した特性を発揮するガラスセラミック焼結体が得られる。
また、本発明のガラスセラミック多層基板によれば、本発明のガラスセラミック原料組成物を焼成してなるガラスセラミック絶縁層、さらにはＡｇ系の導体パターンを備えるので、特性変動が少なく信頼性に優れ、さらに高周波帯域において優れた電気特性を発揮するガラスセラミック多層基板が得られる。
Glass ceramic material composition of the present invention, 20 to 40 wt% of silicon oxide in terms of SiO 2, 30-60 wt% barium oxide in terms of BaO, 5 to 20 wt% of magnesium oxide in terms of MgO, zinc oxide 0-10% by weight calculated as ZnO, 0 to 10% by weight of aluminum oxide in terms of Al 2 O 3, and 50-65 wt% of glass powder containing 0-10 wt% of boron oxide in terms of B 2 O 3, 50-70 wt% of silicon oxide in terms of SiO 2, 10-40 wt% barium oxide in terms of BaO, 0 to 20 wt% of magnesium oxide in terms of MgO, 0 to 15 weight aluminum oxide in terms of Al 2 O 3 % and the ceramic powder 35 to 50 wt% containing, saw including a further, when at least one of cerium oxide titanium oxide, CeO 2 conversion cerium oxide, respectively In 5 wt% or less, and those containing titanium oxide in a proportion of 5 wt% or less in terms of TiO 2, components of BaO · 2MgO · 2SiO 2 main crystalline phase precipitated upon firing this, only a glass In addition, since it is contained in the ceramic, the glass-ceramic sintered body exhibiting stable characteristics can be obtained because the composition of the glass phase hardly changes.
In addition, according to the glass ceramic multilayer substrate of the present invention, the glass ceramic insulating layer formed by firing the glass ceramic raw material composition of the present invention, and further provided with an Ag-based conductor pattern, have little characteristic variation and excellent reliability. Furthermore, a glass ceramic multilayer substrate that exhibits excellent electrical characteristics in a high frequency band can be obtained.
まず、本発明のガラスセラミック原料組成物ならびにガラスセラミック焼結体について説明する。 First, the glass ceramic raw material composition and the glass ceramic sintered body of the present invention will be described.
本発明のガラスセラミック原料組成物は、
・酸化ケイ素をＳｉＯ2換算で２０〜４０重量％、酸化バリウムをＢａＯ換算で３０〜６０重 量％、酸化マグネシウムをＭｇＯ換算で５〜２０重量％、酸化亜鉛をＺｎＯ換算で０〜１０ 重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１０重量％、酸化ホウ素をＢ2Ｏ3換算 で０〜１０重量％含有するガラス粉末（Ａ）と、
・酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重 量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換 算で０〜１５重量％含有するセラミック粉末（Ｂ）と、
を含むものである。そして、本発明のガラスセラミック焼結体は、このガラスセラミック原料粉末を所望の形状に成形し、焼成してなるものであって、ＢａＯ・２ＭｇＯ・２ＳｉＯ2を主とする結晶相を析出している。
The glass ceramic raw material composition of the present invention is
- 20 to 40 wt% of silicon oxide in terms of SiO 2, 30-60 by weight% barium oxide in terms of BaO, 5 to 20 wt% of magnesium oxide in terms of MgO, 0 to 10 wt% of zinc oxide calculated as ZnO Glass powder (A) containing 0 to 10 wt% of aluminum oxide in terms of Al 2 O 3 and 0 to 10 wt% of boron oxide in terms of B 2 O 3 ;
- 50 to 70 wt% of silicon oxide in terms of SiO 2, 10 to 40 by weight% barium oxide in terms of BaO, magnesium oxide 0-20 wt% in terms of MgO, an oxide of aluminum with Al 2 O 3 conversion calculated 0 Ceramic powder (B) containing -15 wt%,
Is included. The glass ceramic sintered body of the present invention is obtained by molding this glass ceramic raw material powder into a desired shape and firing it, and depositing a crystal phase mainly composed of BaO.2MgO.2SiO 2. Yes.
ここで、本発明のガラスセラミック原料組成物におけるガラス粉末（Ａ）の組成限定理由を説明する。 Here, the reason for limiting the composition of the glass powder (A) in the glass ceramic raw material composition of the present invention will be described.
ガラス粉末（Ａ）中の酸化ケイ素は、ガラス粉末の２０〜４０重量％を占めている必要がある。酸化ケイ素の含有量がＳｉＯ2換算で２０重量％未満であると、得られるガラスセラミック焼結体の結晶化度が低下し、そのＱ値が低下する。特に、本発明においては、このガラス粉末がセラミック粉末と反応し、あるいは、ガラス中に、ＢａＯ・２ＭｇＯ・２ＳｉＯ2（ＢａＭｇ2Ｓｉ2Ｏ7）主結晶相、さらにはＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2（ＢａＡｌ2Ｓｉ2Ｏ8）副結晶相を析出し得るが、これらの結晶相の析出に伴い、ガラスセラミック焼結体のガラス相におけるＳｉＯ2成分が減少し、得られるガラスセラミック焼結体の耐湿性が低下する。他方、酸化ケイ素の含有量がＳｉＯ2換算で４０重量％を超えると、ガラスの粘性が高くなり、ガラスセラミック焼結体が十分に焼結しない。なお、ガラス粉末中の酸化ケイ素の含有量は２５〜３５重量％が望ましい。 The silicon oxide in the glass powder (A) needs to occupy 20 to 40% by weight of the glass powder. When the content of silicon oxide is less than 20% by weight in terms of SiO 2 , the crystallinity of the obtained glass ceramic sintered body is lowered, and the Q value is lowered. Particularly, in the present invention, the glass powder will react with the ceramic powder, or in the glass, BaO · 2MgO · 2SiO 2 ( BaMg 2 Si 2 O 7) main crystal phase, more BaO · Al 2 O 3 · 2SiO 2 (BaAl 2 Si 2 O 8 ) sub-crystal phase can be precipitated, but with the precipitation of these crystal phases, the SiO 2 component in the glass phase of the glass-ceramic sintered body decreases, and the resulting glass-ceramic sintered Reduces moisture resistance of the body. On the other hand, when the content of silicon oxide exceeds 40% by weight in terms of SiO 2 , the viscosity of the glass increases and the glass ceramic sintered body is not sufficiently sintered. The content of silicon oxide in the glass powder is preferably 25 to 35% by weight.
また、ガラス粉末（Ａ）中の酸化バリウムは、ガラス粉末の３０〜６０重量％を占めている必要がある。
この酸化バリウムは、後述する酸化マグネシウムや酸化アルミニウムと同様に、ガラスセラミック焼結体中に析出するＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相やＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2結晶相の構成成分であり、これらの結晶相の析出量を制御することで、ガラスセラミック焼結体の熱膨張係数がコントロールされる。
なお、酸化バリウムの含有量がＢａＯ換算で３０重量％未満であると、主結晶相であるＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相や副結晶相であるＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2結晶相の析出量が低下し、ガラスセラミック焼結体のＱ値が低下する。
他方、酸化バリウムの含有量がＢａＯ換算で６０重量％を超えると、結晶相が析出した後のガラス相において、酸化バリウムが相当量残留し、これに伴って、ガラスセラミック焼結体の耐湿性が低下する。
ガラス粉末中の酸化バリウムの含有量は３５〜５５重量％が望ましい。
Moreover, the barium oxide in glass powder (A) needs to occupy 30 to 60 weight% of glass powder.
The barium oxide, like magnesium oxide or aluminum oxide, which will be described later, be a constituent of BaO · 2MgO · 2SiO 2 crystal phase and BaO · Al 2 O 3 · 2SiO 2 crystal phase precipitating in the glass ceramic sintered body The thermal expansion coefficient of the glass ceramic sintered body is controlled by controlling the amount of precipitation of these crystal phases.
Incidentally, the content of barium oxide is less than 30 wt% in terms of BaO, of BaO · Al 2 O 3 · 2SiO 2 crystal phase is BaO · 2MgO · 2SiO 2 crystalline phase and sub crystalline phase is the main crystal phase The amount of precipitation decreases, and the Q value of the glass ceramic sintered body decreases.
On the other hand, when the content of barium oxide exceeds 60% by weight in terms of BaO, a considerable amount of barium oxide remains in the glass phase after the crystal phase is precipitated, and accompanying this, the moisture resistance of the glass ceramic sintered body Decreases.
The content of barium oxide in the glass powder is preferably 35 to 55% by weight.
また、ガラス粉末（Ａ）中の酸化ホウ素は、ガラス粉末の０〜１０重量％とする必要がある。この酸化ホウ素は主に融剤として作用するものである。ガラス粉末中に酸化ホウ素が含まれていなくてもよいが、ガラスの軟化温度を下げ、その粘性流動を促進するために、０．０１重量％以上含まれていることが望ましい。なお、酸化ホウ素の含有量がＢ2Ｏ3換算で１０重量％を超えると、ガラスセラミック焼結体の耐湿性が低下するとともに、ホウ素がめっき液に溶出しやすくなって、ガラスセラミック焼結体のめっき液に対する耐溶出性が低下する。ガラス粉末中の酸化ホウ素の含有量は２〜８重量％がさらに望ましい。 Moreover, the boron oxide in glass powder (A) needs to be 0-10 weight% of glass powder. This boron oxide mainly acts as a flux. Although boron oxide may not be contained in the glass powder, it is preferably contained in an amount of 0.01% by weight or more in order to lower the softening temperature of the glass and promote its viscous flow. When the content of boron oxide exceeds 10% by weight in terms of B 2 O 3 , the moisture resistance of the glass ceramic sintered body is lowered, and boron is easily eluted into the plating solution. The elution resistance to the plating solution decreases. The content of boron oxide in the glass powder is more preferably 2 to 8% by weight.
また、ガラス粉末（Ａ）中の酸化マグネシウムは、ガラス粉末の５〜２０重量％を占めている必要がある。この酸化マグネシウムは、ガラスの溶融温度を下げる作用を有するとともに、主結晶相であるＢａＯ・２ＭｇＯ・２ＳｉＯ2の構成成分である。このＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相は、得られるガラスセラミック焼結体の熱膨張係数を高くすることができ、その含有量がＭｇＯ換算で５重量％未満であると、主結晶相の析出量が少なく、特に、ガラスセラミック焼結体の熱膨張係数が９ｐｐｍ／℃より低くなることがある。他方、その含有量がＭｇＯ換算で２０重量％を超えると、主結晶相の析出量が多くなりすぎ、特に、ガラスセラミック焼結体の熱膨張係数が１２ｐｐｍ／℃より高くなることがある。なお、ガラス粉末中の酸化マグネシウムの含有量は８〜１７重量％がさらに望ましい。 Moreover, the magnesium oxide in glass powder (A) needs to occupy 5 to 20 weight% of glass powder. This magnesium oxide has a function of lowering the melting temperature of the glass and is a constituent component of BaO.2MgO.2SiO 2 which is the main crystal phase. This BaO · 2MgO · 2SiO 2 crystal phase can increase the thermal expansion coefficient of the obtained glass-ceramic sintered body, and if the content is less than 5% by weight in terms of MgO, the amount of precipitated main crystal phase In particular, the thermal expansion coefficient of the glass ceramic sintered body may be lower than 9 ppm / ° C. On the other hand, when the content exceeds 20% by weight in terms of MgO, the amount of precipitation of the main crystal phase becomes excessive, and in particular, the thermal expansion coefficient of the glass ceramic sintered body may be higher than 12 ppm / ° C. The content of magnesium oxide in the glass powder is more preferably 8 to 17% by weight.
また、ガラス粉末（Ａ）中の酸化亜鉛は、ガラス粉末の０〜１０重量％とする必要がある。この酸化マグネシウムは、ガラス作製時の溶融温度を下げる作用を有する。ガラス粉末中に酸化亜鉛が含まれていなくてもよいが、ガラス粉末を作製しやすくするため、０．０１重量％以上含まれていることが望ましい。なお、酸化亜鉛の含有量がＺｎＯ換算で１０重量％を超えると、ガラスセラミック焼結体の耐湿性が低下するとともに、亜鉛がめっき液に溶出しやすくなって、ガラスセラミック焼結体のめっき液に対する耐溶出性が低下する。ガラス粉末中の酸化亜鉛の含有量は２〜８重量％がさらに望ましい。 Moreover, the zinc oxide in glass powder (A) needs to be 0-10 weight% of glass powder. This magnesium oxide has the effect | action which lowers | hangs the melting temperature at the time of glass preparation. Although zinc oxide may not be contained in the glass powder, it is desirable that it be contained in an amount of 0.01% by weight or more in order to make the glass powder easy to produce. When the content of zinc oxide exceeds 10% by weight in terms of ZnO, the moisture resistance of the glass ceramic sintered body decreases and zinc easily elutes into the plating solution. The elution resistance to is reduced. The content of zinc oxide in the glass powder is more preferably 2 to 8% by weight.
また、ガラス粉末（Ａ）中の酸化アルミニウムは、ガラス粉末の０〜１０重量％とする必要がある。酸化アルミニウムは、ガラスの化学的安定性を向上させるものであり、ガラス粉末中に含まれていなくてもよいが、０．０１重量％以上含まれていることが望ましい。また、酸化アルミニウムは、副結晶相であるＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2の構成成分であるが、この結晶相は、ガラスセラミック焼結体の熱膨張係数を低下させる傾向にあり、その含有量がＡｌ2Ｏ3換算で１０重量％を超えると、特に、ガラスセラミック焼結体の熱膨張係数が９ｐｐｍ／℃より低くなることがあり、さらに、ガラスの粘性が高くなる傾向にあるため、得られるガラスセラミック焼結体が十分に焼結しない。なお、ガラス粉末中の酸化アルミニウムの含有量は２〜８重量％がさらに望ましい。 Moreover, the aluminum oxide in glass powder (A) needs to be 0 to 10 weight% of glass powder. Aluminum oxide improves the chemical stability of the glass and may not be contained in the glass powder, but is desirably contained in an amount of 0.01% by weight or more. Aluminum oxide is a constituent component of BaO.Al 2 O 3 .2SiO 2 which is a sub-crystal phase, but this crystal phase tends to lower the thermal expansion coefficient of the glass ceramic sintered body, and its inclusion When the amount exceeds 10% by weight in terms of Al 2 O 3 , the thermal expansion coefficient of the glass ceramic sintered body may be lower than 9 ppm / ° C., and the viscosity of the glass tends to increase. The obtained glass ceramic sintered body does not sinter sufficiently. The content of aluminum oxide in the glass powder is more preferably 2 to 8% by weight.
次に、本発明のガラスセラミック原料組成物におけるセラミック粉末（Ｂ）の組成限定理由を説明する。 Next, the reason for limiting the composition of the ceramic powder (B) in the glass ceramic raw material composition of the present invention will be described.
セラミック粉末（Ｂ）の主成分は酸化ケイ素であり、酸化ケイ素はセラミック粉末の５０〜７０重量％を占めている必要がある。セラミック粉末中のＳｉＯ2は、ＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相やＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2結晶相の一構成成分に変化すると考えられ、その含有量が５０重量％未満であると、得られるガラスセラミック焼結体の結晶化度が低下し、そのＱ値が小さくなる。さらに、セラミック粉末中のＳｉＯ2は、焼成過程でガラス中に溶解し、Ｓｉを構成成分とする結晶相が析出した場合のガラス中のＳｉＯ2量が低下するのを抑制する役割を果たすと考えられ、その含有量が５０重量％未満であると、ガラス中のＳｉ成分量の低下を補うことができないため、ガラス相の耐湿性、つまりは、ガラスセラミック焼結体の耐湿性が低下する。他方、酸化ケイ素の含有量が７０重量％を超えると、ガラスの粘性が高くなり、得られるガラスセラミック焼結体が十分に焼結しない。なお、セラミック粉末中の酸化ケイ素の含有量は５５〜６５重量％が望ましい。 The main component of the ceramic powder (B) is silicon oxide, and the silicon oxide needs to account for 50 to 70% by weight of the ceramic powder. The SiO 2 in the ceramic powder is considered to change into a constituent component of the BaO · 2MgO · 2SiO 2 crystal phase or the BaO · Al 2 O 3 · 2SiO 2 crystal phase, and the content thereof is less than 50% by weight, The crystallinity of the obtained glass ceramic sintered body is lowered, and the Q value is reduced. Further, SiO 2 in the ceramic powder is considered to play a role of suppressing the decrease in the amount of SiO 2 in the glass when it dissolves in the glass during the firing process and a crystal phase containing Si as a constituent component is precipitated. If the content is less than 50% by weight, the decrease in the amount of Si component in the glass cannot be compensated, so that the moisture resistance of the glass phase, that is, the moisture resistance of the glass ceramic sintered body is decreased. On the other hand, when the content of silicon oxide exceeds 70% by weight, the viscosity of the glass increases, and the obtained glass ceramic sintered body is not sufficiently sintered. The content of silicon oxide in the ceramic powder is preferably 55 to 65% by weight.
上述のように、セラミック粉末は、焼成過程にてその成分の一部がガラス中に溶解して、ガラスの成分組成を変化させる。つまり、ガラスセラミック焼結体にて析出するＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相の析出量やガラス相の組成は、ガラス粉末の組成のみではなく、セラミック粉末の組成にも影響されるため、この点から、酸化ケイ素、酸化バリウム、酸化マグネシウム等の組成を決定する必要がある。 As described above, a part of the components of the ceramic powder is dissolved in the glass during the firing process, and the component composition of the glass is changed. In other words, the precipitation amount of the BaO · 2MgO · 2SiO 2 crystal phase and the composition of the glass phase precipitated in the glass ceramic sintered body are affected not only by the composition of the glass powder but also by the composition of the ceramic powder. Therefore, it is necessary to determine the composition of silicon oxide, barium oxide, magnesium oxide and the like.
また、セラミック粉末（Ｂ）の酸化バリウムは、セラミック粉末の１０〜４０重量％を占めている必要がある。セラミック粉末中の酸化バリウムは、焼成過程において、ガラス中に部分的に溶解し、ガラス中の酸化バリウム量を増大させる。上述したように、ガラスセラミック焼結体に析出する主結晶相はＢａＯ・２ＭｇＯ・２ＳｉＯ2であり、特に、この結晶相の析出量を制御することで、ガラスセラミック焼結体の熱膨張係数をコントロールすることができる。なお、酸化バリウムの含有量が１０重量％未満であると、ＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相やＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2結晶相の析出量が不足し、ガラスセラミック焼結体のＱ値が低下する。他方、その含有量が４０重量％を超えると、結晶が析出した後のガラス相において、酸化バリウムが相当量残ってしまい、それに伴って、ガラスセラミック焼結体の耐湿性が低下する。セラミック粉末中の酸化バリウムの含有量は１５〜３５重量％が望ましい。 Moreover, the barium oxide of ceramic powder (B) needs to occupy 10 to 40 weight% of ceramic powder. Barium oxide in the ceramic powder is partially dissolved in the glass during the firing process, increasing the amount of barium oxide in the glass. As described above, the main crystal phase precipitated on the glass ceramic sintered body is BaO.2MgO.2SiO 2 , and in particular, by controlling the amount of precipitation of this crystal phase, the thermal expansion coefficient of the glass ceramic sintered body can be increased. Can be controlled. Incidentally, the content of barium oxide is less than 10 wt%, insufficient precipitation amount of BaO · 2MgO · 2SiO 2 crystal phase and BaO · Al 2 O 3 · 2SiO 2 crystal phase, a glass ceramic sintered body Q The value drops. On the other hand, when the content exceeds 40% by weight, a considerable amount of barium oxide remains in the glass phase after the crystals are precipitated, and accordingly, the moisture resistance of the glass ceramic sintered body is lowered. The content of barium oxide in the ceramic powder is preferably 15 to 35% by weight.
また、セラミック粉末（Ｂ）の酸化マグネシウムは、セラミック粉末の０〜２０重量％とする必要がある。セラミック粉末中の酸化マグネシウムは、焼成過程において、ガラス中に部分的に溶解し、ガラス中の酸化マグネシウム量を増大させるものであり、セラミック粉末中に含まれていなくてもよいが、０．０１重量％以上含まれていることが望ましい。なお、この酸化マグネシウムは、ガラス作製時の溶融温度を下げる作用を有するとともに、主結晶相であるＢａＯ・２ＭｇＯ・２ＳｉＯ2の構成成分として機能する。このＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相は、得られるガラスセラミック焼結体の熱膨張係数を高くするものであり、酸化マグネシウムの含有量がＭｇＯ換算で２０重量％を超えると、主結晶相の析出量が多くなりすぎ、特に、ガラスセラミック焼結体の熱膨張係数が１２ｐｐｍ／℃より高くなることがある。セラミック粉末中の酸化マグネシウムの含有量は５〜１５重量％がさらに望ましい。 Further, the magnesium oxide of the ceramic powder (B) needs to be 0 to 20% by weight of the ceramic powder. Magnesium oxide in the ceramic powder is partially dissolved in the glass in the firing process to increase the amount of magnesium oxide in the glass, and may not be contained in the ceramic powder. It is desirable that it is contained by weight% or more. Incidentally, the magnesium oxide has an effect of lowering the melting temperature during glass making, functions as a component of BaO · 2MgO · 2SiO 2 is a main crystalline phase. This BaO · 2MgO · 2SiO 2 crystal phase increases the thermal expansion coefficient of the obtained glass ceramic sintered body. When the content of magnesium oxide exceeds 20% by weight in terms of MgO, the main crystal phase is precipitated. The amount becomes too large, and in particular, the thermal expansion coefficient of the glass ceramic sintered body may be higher than 12 ppm / ° C. The content of magnesium oxide in the ceramic powder is more preferably 5 to 15% by weight.
また、セラミック粉末（Ｂ）の酸化アルミニウムは、セラミック粉末の０〜１５重量％とする必要がある。セラミック粉末中の酸化アルミニウムは、焼成過程において、ガラス中に部分的に溶解し、ガラス中の酸化アルミニウム量を増大させ、ガラスの化学的安定性を向上させるものである。酸化アルミニウムは、セラミック粉末中に全く含まれていなくてもよいが、０．０１重量％以上含まれていることが望ましい。なお、酸化アルミニウムは、ＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2副結晶相の構成成分であるが、この結晶相は、ガラスセラミック焼結体の熱膨張係数を低下させる傾向にあり、その含有量がＡｌ2Ｏ3換算で１５重量％を超えると、特に、ガラスセラミック焼結体の熱膨張係数が９ｐｐｍ／℃より低くなることがあり、さらに、ガラスの粘性が高くなる傾向にあるため、得られるガラスセラミック焼結体が十分に焼結しない。なお、セラミック粉末中の酸化アルミニウムの含有量は３〜１２重量％がさらに望ましい。 Moreover, the aluminum oxide of the ceramic powder (B) needs to be 0 to 15% by weight of the ceramic powder. Aluminum oxide in the ceramic powder is partially dissolved in the glass in the firing process, increases the amount of aluminum oxide in the glass, and improves the chemical stability of the glass. Aluminum oxide may not be contained in the ceramic powder at all, but is desirably contained in an amount of 0.01% by weight or more. Aluminum oxide is a constituent component of the BaO.Al 2 O 3 .2SiO 2 subcrystalline phase, but this crystalline phase tends to lower the thermal expansion coefficient of the glass ceramic sintered body, and its content is When it exceeds 15% by weight in terms of Al 2 O 3 , the thermal expansion coefficient of the glass-ceramic sintered body may be lower than 9 ppm / ° C., and the viscosity of the glass tends to increase. The glass ceramic sintered body does not sinter sufficiently. The content of aluminum oxide in the ceramic powder is more preferably 3 to 12% by weight.
本発明において、ガラスセラミック原料組成物は、ガラス粉末を５０〜６５重量％、セラミック粉末を３５〜５０重量％含有する。
ガラス粉末の含有量が５０重量％未満であり、セラミック粉末の含有量が５０重量％を超えると、セラミック焼結体を十分に焼結することが困難であり、また、セラミック焼結体の耐湿性が低下する傾向があり、他方、ガラス粉末の含有量が６５重量％を超え、セラミック粉末の含有量が３５重量％未満であると、セラミック焼結体の熱膨張係数が小さくなる傾向がある。
なお、ガラス粉末の含有量は５３〜６２重量％、セラミック粉末の含有量は３８〜４７重量％がさらに望ましい。
In the present invention, a glass ceramic material composition, glass powder 50-65 wt%, you containing ceramic powder 35-50% by weight.
When the content of the glass powder is less than 50% by weight and the content of the ceramic powder exceeds 50% by weight, it is difficult to sufficiently sinter the ceramic sintered body. On the other hand, if the content of the glass powder exceeds 65% by weight and the content of the ceramic powder is less than 35% by weight, the thermal expansion coefficient of the ceramic sintered body tends to be small. .
The glass powder content is more preferably 53 to 62% by weight, and the ceramic powder content is more preferably 38 to 47% by weight.
また、本発明において、ガラスセラミック原料組成物は、上述したガラス粉末およびセラミック粉末に加えて、さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有する。
酸化セリウムは酸化剤としての役割を有しており、脱バインダ時の残留炭素量の低下、さらには、Ａｇ系導体パターンと同時焼成したときの黄着色化の防止に寄与する。
酸化チタンの含有量がガラスセラミック原料組成物の５重量％を超えると、Ａｇを主成分とする導体パターンの表面に無電解めっきあるいは電解めっきを施すに際し、ガラスセラミック焼結体（素体）の表面にまで、めっき膜が異常析出することがある。
また、酸化チタンは、得られるガラスセラミック焼結体の強度向上に寄与するものであるが、その含有量がガラスセラミック原料組成物の５重量％を超えると、ガラスセラミック焼結体のＱ値が低下し、高周波帯域における損失が大きくなる傾向にある。
Further, in the present invention, a glass ceramic material composition, in addition to the glass powder and ceramic powder described above, further, in the case where at least one of cerium oxide titanium oxide, 5 weight respectively cerium oxide in terms of CeO 2 % Or less, and titanium oxide is contained at a ratio of 5% by weight or less in terms of TiO 2 .
Cerium oxide has a role as an oxidizing agent, and contributes to a reduction in the amount of residual carbon at the time of binder removal and further prevention of yellowing when co-fired with an Ag-based conductor pattern.
When the content of titanium oxide exceeds 5% by weight of the glass ceramic raw material composition, when the electroless plating or electrolytic plating is performed on the surface of the conductor pattern mainly composed of Ag, the glass ceramic sintered body (element body) The plating film may be deposited abnormally to the surface.
Moreover, although titanium oxide contributes to the strength improvement of the glass ceramic sintered compact obtained, when the content exceeds 5 weight% of a glass ceramic raw material composition, Q value of a glass ceramic sintered compact will become. It tends to decrease and the loss in the high frequency band tends to increase.
次に、本発明のガラスセラミック多層基板を、図１を参照に、説明する。 Next, the glass ceramic multilayer substrate of the present invention will be described with reference to FIG.
図１に示すガラスセラミック多層基板１は、本発明のガラスセラミック原料組成物を焼成してなり、主結晶相としてＢａＯ・２ＭｇＯ・２ＳｉＯ2結晶相を析出した複数のガラスセラミック絶縁層２と、この複数のガラスセラミック絶縁層の間に設けられたＡｇ系導体パターンとを備える。 A glass ceramic multilayer substrate 1 shown in FIG. 1 is obtained by firing a glass ceramic raw material composition of the present invention, and a plurality of glass ceramic insulating layers 2 in which a BaO.2MgO.2SiO 2 crystal phase is precipitated as a main crystal phase. And an Ag-based conductor pattern provided between the plurality of glass ceramic insulating layers.
ガラスセラミック多層基板１の一方主面３ａには、Ａｇを主成分とする表面導体パターン４が形成されている。表面導体パターン４上には、シリコンやＧａＡｓ等の半導体デバイス８ａ、８ｃ、チップ型積層コンデンサ８ｂ等の表面実装部品が、はんだを介して接続されている。また、ガラスセラミック多層基板１の他方主面３ｂには、Ａｇを主成分とする表面導体パターン５が形成されており、この表面導体パターン５は、ガラスセラミック多層基板１を図示しないマザーボード（プリント配線基板）に電気的に接続するための外部端子電極としての役割を果たす。これらのＡｇ系導体パターンは、タングステンやモリブデン等の高融点金属に比べて比抵抗が小さく、高周波帯域においても優れた電気伝導性を示す。なお、表面導体パターン４、６の表面には、ＮｉやＡｕ等のめっき膜が形成されていてもよい。 On one main surface 3a of the glass ceramic multilayer substrate 1, a surface conductor pattern 4 mainly composed of Ag is formed. On the surface conductor pattern 4, surface mount components such as semiconductor devices 8a and 8c such as silicon and GaAs, chip type multilayer capacitors 8b, and the like are connected via solder. Further, a surface conductor pattern 5 mainly composed of Ag is formed on the other main surface 3b of the glass ceramic multilayer substrate 1, and this surface conductor pattern 5 is formed on a mother board (printed wiring) that does not illustrate the glass ceramic multilayer substrate 1. It serves as an external terminal electrode for electrical connection to the substrate. These Ag-based conductor patterns have a lower specific resistance than refractory metals such as tungsten and molybdenum, and exhibit excellent electrical conductivity even in a high frequency band. A plating film such as Ni or Au may be formed on the surface of the surface conductor patterns 4 and 6.
また、ガラスセラミック多層基板１において、複数のガラスセラミック絶縁層２の間には、内部導体パターン６、７が設けられている。内部導体パターン６は、各ガラスセラミック絶縁層３の界面に配置された面内導体であり、内部導体パターン７は、各ガラスセラミック絶縁層３を貫通し、面内導体同士を三次元的に接続するためのビア導体である。この内部導体パターン６、７により、ガラスセラミック多層基板１内に、インダクタンス素子やキャパシタ素子等の受動素子や配線導体が形成されている。 In the glass ceramic multilayer substrate 1, internal conductor patterns 6 and 7 are provided between the plurality of glass ceramic insulating layers 2. The internal conductor pattern 6 is an in-plane conductor disposed at the interface of each glass ceramic insulating layer 3, and the internal conductor pattern 7 penetrates each glass ceramic insulating layer 3 to connect the in-plane conductors in a three-dimensional manner. This is a via conductor. With the internal conductor patterns 6 and 7, passive elements such as inductance elements and capacitor elements and wiring conductors are formed in the glass ceramic multilayer substrate 1.
そして、各ガラスセラミック絶縁層２には、ＢａＯ・２ＭｇＯ・２ＳｉＯ2（ＢａＭｇ2Ｓｉ2Ｏ7）を主とする結晶相（主結晶相）、さらにはＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2（ＢａＡｌ2Ｓｉ2Ｏ8）からなる結晶相（副結晶相）が析出している。これらの結晶相の析出は、ガラスセラミック絶縁層２の熱膨張係数の制御、Ｑ値の向上、比誘電率の制御等に大きく寄与するものである。 Each glass ceramic insulating layer 2 has a crystal phase (main crystal phase) mainly composed of BaO.2MgO.2SiO 2 (BaMg 2 Si 2 O 7 ), and further BaO.Al 2 O 3 .2SiO 2 (BaAl 2 Si 2 O 8 ) is precipitated. Precipitation of these crystal phases greatly contributes to control of the thermal expansion coefficient of the glass ceramic insulating layer 2, improvement of the Q value, control of the dielectric constant, and the like.
ガラスセラミック多層基板１は、以下のような方法により作製される。 The glass ceramic multilayer substrate 1 is produced by the following method.
まず、ＳｉＯ2、ＢａＣＯ3、Ｍｇ（ＯＨ）2、ＺｎＯ、Ａｌ2Ｏ3、Ｂ2Ｏ3等の原料粉末を、所定の割合で秤量し、得られた混合物をるつぼにて溶融し、得られたガラス融液を急冷して、ガラスカレットを作製する。次いで、得られたガラスカレットを粗粉砕し、さらにボールミル等を用いて微粉砕することによって、ガラス粉末（Ａ）を得る。 First, raw material powders such as SiO 2 , BaCO 3 , Mg (OH) 2 , ZnO, Al 2 O 3 , B 2 O 3 are weighed at a predetermined ratio, and the resulting mixture is melted in a crucible. The obtained glass melt is rapidly cooled to produce a glass cullet. Next, the obtained glass cullet is roughly pulverized and further finely pulverized using a ball mill or the like to obtain glass powder (A).
他方、ＳｉＯ2、ＢａＣＯ3、Ｍｇ（ＯＨ）2、Ａｌ2Ｏ3等の原料粉末を、所定の割合で秤量し、得られた混合物を仮焼した後、ボールミル等で微粉砕することによって、セラミック粉末（Ｂ）を得る。 On the other hand, raw material powders such as SiO 2 , BaCO 3 , Mg (OH) 2 , Al 2 O 3 are weighed at a predetermined ratio, and the resulting mixture is calcined and then finely pulverized with a ball mill or the like. A ceramic powder (B) is obtained.
そして、ガラス粉末（Ａ）およびセラミック粉末（Ｂ）、さらに必要に応じて、酸化セリウムや酸化チタンを所定の重量比となるように混合する。 Then, the glass powder (A) and the ceramic powder (B) and, if necessary, cerium oxide and titanium oxide are mixed so as to have a predetermined weight ratio.
次に、得られた混合粉末に、トルエン、キシレン、アルコール等の溶剤、アクリル樹脂やブチラール樹脂等のバインダ、ジブチルフタレートやジコクチルフタレート等の可塑剤を加えて混練し、スラリーを作製する。次に、このスラリーをドクターブレード法によりシート状に成形して、焼成後にガラスセラミック絶縁層となるセラミックグリーンシートを作製する。なお、たとえば、溶剤は、ガラス粉末（Ａ）およびセラミック粉末（Ｂ）の混合粉末１００重量部に対して１〜３０重量部、バインダは３〜３０重量部、をそれぞれ加えることができる。 Next, a solvent such as toluene, xylene and alcohol, a binder such as acrylic resin and butyral resin, and a plasticizer such as dibutyl phthalate and dioctyl phthalate are added to the obtained mixed powder and kneaded to prepare a slurry. Next, this slurry is formed into a sheet shape by a doctor blade method to produce a ceramic green sheet that becomes a glass ceramic insulating layer after firing. For example, 1 to 30 parts by weight of the solvent can be added to 100 parts by weight of the mixed powder of the glass powder (A) and the ceramic powder (B), and 3 to 30 parts by weight of the binder can be added.
次に、上記のセラミックグリーンシートにビア導体形成用孔をパンチングやレーザー加工等によって形成し、この孔に、Ａｇ粉末を主とするＡｇ系導電性ペーストを充填する。その後、Ａｇ粉末を主とするＡｇ系導電性ペーストをスクリーン印刷によって所定パターンとなるように印刷する。 Next, a hole for forming a via conductor is formed in the ceramic green sheet by punching, laser processing, or the like, and an Ag-based conductive paste mainly containing Ag powder is filled in the hole. Thereafter, an Ag-based conductive paste mainly containing Ag powder is printed by screen printing so as to form a predetermined pattern.
次に、得られたセラミックグリーンシートを所定枚数積層して、導体パターンおよびビア導体が形成されたセラミック積層体を作製する。次に、プレス機によりセラミック積層体を圧着した後、空気中等の酸化性雰囲気中、７８０〜１０００℃、特に具体的に言えば９００℃、で焼成する。なお、表面導体パターンは、セラミック積層体と同時焼成することにより形成してもよいし、セラミック積層体の焼成後、焼き付けることによって形成してもよい。また、表面導体パターンの表面には、ＮｉやＡｕ等のめっき膜を無電解めっき法や電解めっき法に基づいて形成することが好ましい。その後、半導体デバイスやチップ型積層コンデンサ等の表面実装部品を、表面導体パターンにはんだ等の導電材を介して接続することによって、図１に示すセラミック多層基板１が得られる。 Next, a predetermined number of the obtained ceramic green sheets are laminated to produce a ceramic laminate in which conductor patterns and via conductors are formed. Next, after the ceramic laminate is pressure-bonded by a press machine, it is fired at 780 to 1000 ° C., more specifically 900 ° C. in an oxidizing atmosphere such as air. The surface conductor pattern may be formed by simultaneous firing with the ceramic laminate, or may be formed by baking after firing the ceramic laminate. Moreover, it is preferable to form a plating film such as Ni or Au on the surface of the surface conductor pattern based on an electroless plating method or an electrolytic plating method. Thereafter, a surface-mounted component such as a semiconductor device or a chip-type multilayer capacitor is connected to the surface conductor pattern via a conductive material such as solder, whereby the ceramic multilayer substrate 1 shown in FIG. 1 is obtained.
なお、得られたガラスセラミック絶縁層には、上述したように、ＢａＯ・２ＭｇＯ・２ＳｉＯ2（ＢａＭｇ2Ｓｉ2Ｏ7）主結晶相、さらにはＢａＯ・Ａｌ2Ｏ3・２ＳｉＯ2（ＢａＡｌ2Ｓｉ2Ｏ8）副結晶相が析出している。すなわち、本発明によれば、これら結晶相の構成成分が、ガラスだけでなく、セラミック中にも含まれているので、ガラス相の組成が変動しにくく、特性変動が少なく信頼性に優れ、さらに高周波帯域において優れた電気特性を発揮するガラスセラミック多層基板が得られる。 Incidentally, resulting in the glass ceramic insulating layer, as described above, BaO · 2MgO · 2SiO 2 ( BaMg 2 Si 2 O 7) main crystal phase, more BaO · Al 2 O 3 · 2SiO 2 (BaAl 2 Si 2 O 8 ) Subcrystalline phase is precipitated. That is, according to the present invention, the constituents of the crystal phase are contained not only in the glass but also in the ceramic, so that the composition of the glass phase is less likely to fluctuate, the characteristic variation is small, and the reliability is excellent. A glass ceramic multilayer substrate that exhibits excellent electrical characteristics in a high frequency band can be obtained.
以上、本発明のガラスセラミック多層基板を具体的な構成に基づいて説明したが、本発明のガラスセラミック基板は、上述の構成に限定されるものではない。 As mentioned above, although the glass ceramic multilayer substrate of this invention was demonstrated based on the specific structure, the glass ceramic substrate of this invention is not limited to the above-mentioned structure.
たとえば、本発明のガラスセラミック多層基板は、上述したごとき、その主面に各種の表面実装部品を搭載し、その内部にインダクタやコンデンサ、さらには抵抗を有するような機能基板であってもよいし、あるいは、表面実装部品が搭載されていない単機能部品用基板であってもよい。 For example, as described above, the glass ceramic multilayer substrate of the present invention may be a functional substrate having various surface mount components mounted on the main surface thereof, an inductor, a capacitor, and further a resistor inside. Alternatively, it may be a single-function component substrate on which no surface mount component is mounted.
このように、本発明のガラスセラミック多層基板は、信頼性や高周波特性に優れているので、たとえば、自動車電話、業務用・家庭用無線機器、携帯電話機器等のように、各種マイクロ波・ミリ波対応の電子部品用基板として好適に用いられる。 As described above, since the glass ceramic multilayer substrate of the present invention is excellent in reliability and high frequency characteristics, various microwaves / millimeters such as automobile phones, commercial / home wireless devices, mobile phone devices and the like are used. It is suitably used as a wave-compatible electronic component substrate.
以下、本発明を具体的な実施例に基づいて説明する。 Hereinafter, the present invention will be described based on specific examples.
まず、ＳｉＯ2粉末、ＢａＣＯ3粉末、Ｍｇ（ＯＨ）2粉末、ＺｎＯ粉末、Ａｌ2Ｏ3粉末およびＢ2Ｏ3粉末を、下記表１に示す割合で秤量し、その混合物を白金るつぼにて１５００〜１６００℃で溶融した。その後、得られたガラス融液を急冷ロールに流し出し、ガラスカレットを作製した。次いで、得られたガラスカレットを粗粉砕し、さらにボールミルで微粉砕することによって、下記表１のＧ１〜Ｇ１８で示される組成のガラス粉末を得た。なお、このガラス粉末の平均粒径（Ｄ５０）は１．０〜１．５μｍであった。 First, SiO 2 powder, BaCO 3 powder, Mg (OH) 2 powder, ZnO powder, Al 2 O 3 powder and B 2 O 3 powder were weighed in the proportions shown in Table 1 below, and the mixture was measured in a platinum crucible. It melted at 1500-1600 ° C. Then, the obtained glass melt was poured out to the quenching roll, and the glass cullet was produced. Next, the obtained glass cullet was coarsely pulverized and further finely pulverized with a ball mill to obtain a glass powder having a composition represented by G1 to G18 in Table 1 below. In addition, the average particle diameter (D50) of this glass powder was 1.0-1.5 micrometers.
また、ＳｉＯ2粉末、ＢａＣＯ3粉末、Ｍｇ（ＯＨ）2粉末およびＡｌ2Ｏ3粉末を、下記表２に示す割合で秤量し、その混合物を８００〜１１００℃で仮焼した後、ボールミルで微粉砕することによって、下記表２のＦ１〜Ｆ１２で示される組成のセラミック粉末を得た。なお、このセラミック粉末の平均粒径（Ｄ５０）は１．２〜１．７μｍであった。 In addition, SiO 2 powder, BaCO 3 powder, Mg (OH) 2 powder and Al 2 O 3 powder were weighed in the proportions shown in Table 2 below, and the mixture was calcined at 800 to 1100 ° C. By pulverizing, ceramic powder having a composition represented by F1 to F12 in Table 2 below was obtained. The ceramic powder had an average particle size (D50) of 1.2 to 1.7 μm.
次いで、下記表３に示す割合で、Ｇ１〜Ｇ１８で示される組成のガラス粉末とＦ１〜Ｆ１２で示される組成のセラミック粉末とを混合し、必要に応じて、表３に示す割合のＣｅＯ2粉末、ＴｉＯ2粉末を加え、さらに適量の溶剤、バインダおよび可塑剤を加え、これを十分に混合してスラリー化した後、十分に脱泡し、ドクターブレード法によって、厚さ１００μｍのセラミックグリーンシートを作製した。 Subsequently, the glass powder having the composition indicated by G1 to G18 and the ceramic powder having the composition indicated by F1 to F12 are mixed at the ratio shown in Table 3 below, and the CeO 2 powder having the ratio shown in Table 3 is mixed if necessary. Then, add TiO 2 powder, add appropriate amount of solvent, binder and plasticizer, mix well to make a slurry, thoroughly defoam, and make a ceramic green sheet with a thickness of 100 μm by doctor blade method Produced.
次いで、まず、得られたセラミックグリーンシートを１０枚積層してプレス機により圧着し、空気中、９００℃で３０分間焼成して、Ｑ値、比誘電率εｒ、熱膨張係数α、焼結度等を評価するためのガラスセラミック多層基板を得た。また、得られたセラミックグリーンシート上にスクリーン印刷によりＡｇペーストを印刷し、これを１０ｍｍ×１０ｍｍの方形状にカットした後、得られたセラミックグリーンシートを１０枚積層してプレス機により圧着し、空気中、９００℃で３０分間焼成することによって、耐湿性を評価するための素子厚み５０μｍのガラスセラミック多層基板（チップ型積層コンデンサ）を得た。 Next, first, 10 ceramic green sheets obtained were laminated and pressure-bonded by a press machine, fired in air at 900 ° C. for 30 minutes, Q value, relative dielectric constant εr, thermal expansion coefficient α, sintering degree. A glass ceramic multilayer substrate for evaluating the above was obtained. Moreover, after printing Ag paste by screen printing on the obtained ceramic green sheet, and cutting this into a 10 mm × 10 mm square shape, 10 sheets of the obtained ceramic green sheets are stacked and pressure-bonded by a press machine, By baking in air at 900 ° C. for 30 minutes, a glass ceramic multilayer substrate (chip type multilayer capacitor) having an element thickness of 50 μm for evaluating moisture resistance was obtained.
次いで、得られたガラスセラミック多層基板について、Ｑ値、比誘電率εｒ、熱膨張係数α、焼結度を測定した。また、得られたチップ型積層コンデンサについて、耐湿性を測定した。 Next, the Q value, relative dielectric constant εr, thermal expansion coefficient α, and degree of sintering of the obtained glass ceramic multilayer substrate were measured. Further, the moisture resistance of the obtained chip type multilayer capacitor was measured.
なお、表３において、Ｑ値および比誘電率εｒは、摂動法により、測定周波数１２ＧＨｚにて測定した値であり、熱膨張係数α（単位ｐｐｍ／℃）は、押棒式熱膨張計を用い、室温〜６００℃で測定した値の平均値である。また、耐湿性は、温度１２１℃、湿度９５％ＲＨの環境下（２ａｔｍ）で１００時間保持後、負荷電圧５０Ｖで絶縁抵抗ＩＲを測定することにより評価した。表３中の値は、ｌｏｇ（ＩＲ／Ω）である。また、焼結度は、ガラスセラミック多層基板の断面の気孔率をＳＥＭ（走査型電子顕微鏡）観察写真の画像解析により測定し、１００％から該気孔率を引いた値である。 In Table 3, Q value and relative dielectric constant εr are values measured by a perturbation method at a measurement frequency of 12 GHz, and a thermal expansion coefficient α (unit: ppm / ° C.) is a push rod type thermal dilatometer. It is the average of the values measured at room temperature to 600 ° C. In addition, the moisture resistance was evaluated by measuring the insulation resistance IR at a load voltage of 50 V after being held for 100 hours in an environment (2 atm) at a temperature of 121 ° C. and a humidity of 95% RH. The values in Table 3 are log (IR / Ω). The degree of sintering is a value obtained by subtracting the porosity from 100% by measuring the porosity of the cross section of the glass ceramic multilayer substrate by image analysis of an SEM (scanning electron microscope) observation photograph.
なお、図示しないが、サンプルＮｏ．Ｆ２のセラミック粉末について、粉末Ｘ線回折法（ＸＲＤ）により、ＳｉＯ2（クォーツ）のピーク値を測定したところ、このセラミック粉末は主結晶相がＳｉＯ2（クォーツ）であることを確認した。 Although not shown, sample no. With respect to the ceramic powder of F2, when the peak value of SiO 2 (quartz) was measured by powder X-ray diffraction (XRD), it was confirmed that the main crystal phase of this ceramic powder was SiO 2 (quartz).
また、サンプルＮｏ．２のガラスセラミック多層基板について、粉末Ｘ線回折法（ＸＲＤ、ターゲット：Ｃｕ、管電圧／管電流＝３５ｋＶ／２５ｍＡ）により、析出した結晶相を同定した結果、図２に示すように、ＢａＯ・２ＭｇＯ・２ＳｉＯ2が主たる結晶相として析出していることを確認できた。 Sample No. 2 was identified by the powder X-ray diffraction method (XRD, target: Cu, tube voltage / tube current = 35 kV / 25 mA). As a result, as shown in FIG. It was confirmed that 2MgO · 2SiO 2 was precipitated as the main crystal phase.
また、サンプルＮｏ．２のガラスセラミック多層基板について、焼成前（５００℃での脱バインダ後）のセラミックグリーンシートにおけるＳｉＯ2（クォーツ）のピーク強度と、焼成後（ガラスセラミック焼結体）におけるＳｉＯ2（クォーツ）のピーク強度と比較した結果、図２に示すように、セラミック粉末に存在したクォーツの約５０％はガラスに溶解もしくは他の結晶相の一構成成分に変化していることを確認した。 Sample No. The second glass ceramic multilayer substrate, before firing of the peak intensity of SiO 2 (quartz) in the ceramic green sheet (removal after the binder at 500 ° C.), after firing SiO 2 in (glass ceramic sintered compact) (Quartz) As a result of comparison with the peak intensity, as shown in FIG. 2, it was confirmed that about 50% of the quartz present in the ceramic powder was dissolved in the glass or changed to one constituent component of the other crystal phase.
表３に示したサンプルＮｏ．２〜３、６〜８、１５〜１８、２０、２６〜３６のガラスセラミック多層基板は、その原料組成物として、酸化ケイ素をＳｉＯ2換算で２０〜４０重量％、酸化バリウムをＢａＯ換算で３０〜６０重量％、酸化マグネシウムをＭｇＯ換算で５〜２０重量％、酸化亜鉛をＺｎＯ換算で０〜１０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１０重量％、酸化ホウ素をＢ2Ｏ3換算で０〜１０重量％含有するガラス粉末５０〜６５重量％と、酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末３５〜５０重量％とを含むガラスセラミック原料組成物が用いられているので、１２ＧＨｚにおけるＱ値：３００以上、比誘電率εｒ：９以下、熱膨張係数α：９〜１２ｐｐｍ／℃、耐湿性（ｌｏｇ（ＩＲ／Ω））：１０以上、焼結度：９７％以上のように、信頼性や高周波特性に優れたガラスセラミック多層基板となった。 Sample No. shown in Table 3 The glass ceramic multilayer substrate of 2 to 3, 6 to 8, 15 to 18, 20, 26 to 36 has, as its raw material composition, 20 to 40% by weight of silicon oxide in terms of SiO 2 and 30 in terms of BaO in terms of BaO. 60 wt%, 5-20 wt% of magnesium oxide in terms of MgO, 0 to 10% by weight of zinc oxide in terms of ZnO, 0 to 10% by weight of aluminum oxide in terms of Al 2 O 3, boron oxide B 2 O 50 to 65% by weight of glass powder containing 0 to 10% by weight in terms of 3; 50 to 70% by weight of silicon oxide in terms of SiO 2 ; 10 to 40% by weight in terms of BaO oxide; and magnesium oxide in terms of MgO. Since a glass ceramic raw material composition containing 0 to 20% by weight and 35 to 50% by weight of ceramic powder containing 0 to 15% by weight of aluminum oxide in terms of Al 2 O 3 is used. Q value at 12 GHz: 300 or more, relative dielectric constant εr: 9 or less, thermal expansion coefficient α: 9 to 12 ppm / ° C., moisture resistance (log (IR / Ω)): 10 or more, sintering degree: 97% or more Thus, a glass ceramic multilayer substrate excellent in reliability and high frequency characteristics was obtained.
なお、ＴｉＯ2の添加量が５重量％を超えたサンプルＮｏ．３３のガラスセラミック多層基板は、Ｑ値が低くなる傾向にあった。また、ＣｅＯ2の添加量が５重量％を超えたサンプルＮｏ．３６のガラスセラミック多層基板においては、Ｐｄ活性化処理後、６０℃の無電解Ｎｉめっき液（奥野製薬製：トップケミアロイＢ−１）に３０分浸漬し、表面電極に無電解Ｎｉめっきを施したところ、ガラスセラミック素体上にもめっきが析出してしまった。すなわち、めっきの異常析出が見られた。 In addition, sample No. in which the addition amount of TiO 2 exceeded 5% by weight. The glass ceramic multilayer substrate No. 33 tended to have a low Q value. In addition, Sample No. in which the addition amount of CeO 2 exceeded 5% by weight. In the 36 glass ceramic multilayer substrate, after Pd activation treatment, it was immersed in an electroless Ni plating solution (Okuno Pharmaceutical Co., Ltd .: Top Chemialloy B-1) at 60 ° C. for 30 minutes, and the surface electrode was subjected to electroless Ni plating. As a result, plating was deposited on the glass ceramic body. That is, abnormal deposition of plating was observed.
また、サンプルＮｏ．１のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＳｉＯ2含有量が少なく、１２ＧＨｚにおけるＱ値が３００を下回ってしまった。他方、サンプルＮｏ．４のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＳｉＯ2含有量が多く、焼結度が低く、また、十分な耐湿性が得られなかった。 Sample No. The glass ceramic multilayer substrate No. 1 had a low SiO 2 content in the glass powder as the raw material composition, and the Q value at 12 GHz was below 300. On the other hand, sample no. The glass ceramic multilayer substrate No. 4 had a high SiO 2 content in the glass powder as the raw material composition, the degree of sintering was low, and sufficient moisture resistance could not be obtained.
また、サンプルＮｏ．５のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＢａＯ含有量が多く、十分な耐湿性が得られなかった。他方、サンプルＮｏ．９のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＢａＯ含有量が少なく、１２ＧＨｚにおけるＱ値が３００を下回ってしまった。 Sample No. The glass ceramic multilayer substrate of No. 5 had a high BaO content in the glass powder as the raw material composition, and sufficient moisture resistance was not obtained. On the other hand, sample no. The glass ceramic multilayer substrate of No. 9 had a low BaO content in the glass powder as the raw material composition, and the Q value at 12 GHz was less than 300.
また、サンプルＮｏ．１０のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＭｇＯ含有量が多く、熱膨張係数αが１２ｐｐｍ／℃を超えてしまった。他方、サンプルＮｏ．１１のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＭｇＯ含有量が少なく、熱膨張係数αが９ｐｐｍ／℃を下回ってしまった。 Sample No. In the glass ceramic multilayer substrate No. 10, the MgO content in the glass powder as the raw material composition was large, and the thermal expansion coefficient α exceeded 12 ppm / ° C. On the other hand, sample no. The glass ceramic multilayer substrate No. 11 had a low MgO content in the glass powder as the raw material composition, and the thermal expansion coefficient α was below 9 ppm / ° C.
また、サンプルＮｏ．１２のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＺｎＯ含有量が多く、十分な耐湿性が得られなかった。また、サンプルＮｏ．１３のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＡｌ2Ｏ3含有量が多く、熱膨張係数αが９ｐｐｍ／℃を下回ってしまい、また、十分な焼結度が得られなかった。 さらに、サンプルＮｏ．１４のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＢ2Ｏ3含有量が多く、十分な耐湿性が得られなかった。 Sample No. No. 12 glass ceramic multilayer substrate had a large ZnO content in the glass powder as the raw material composition, and sufficient moisture resistance could not be obtained. Sample No. The glass ceramic multilayer substrate No. 13 has a high Al 2 O 3 content in the glass powder as the raw material composition, the thermal expansion coefficient α is less than 9 ppm / ° C., and a sufficient degree of sintering cannot be obtained. It was. Furthermore, sample no. No. 14 glass-ceramic multilayer substrate had a large content of B 2 O 3 in the glass powder as the raw material composition, and sufficient moisture resistance was not obtained.
また、サンプルＮｏ．１９のガラスセラミック多層基板は、原料組成物であるセラミック粉末中のＳｉＯ2含有量が少なく、１２ＧＨｚにおけるＱ値が３００を下回ってしまい、また、十分な耐湿性が得られなかった。他方、サンプルＮｏ．２２のガラスセラミック多層基板は、原料組成物であるセラミック粉末中のＳｉＯ2含有量が多く、焼結度が低く、また、十分な耐湿性が得られなかった。 Sample No. The 19 glass-ceramic multilayer substrate had a low SiO 2 content in the ceramic powder as the raw material composition, the Q value at 12 GHz was less than 300, and sufficient moisture resistance was not obtained. On the other hand, sample no. No. 22 glass-ceramic multilayer substrate had a large SiO 2 content in the ceramic powder as the raw material composition, had a low degree of sintering, and could not obtain sufficient moisture resistance.
また、サンプルＮｏ．２３のガラスセラミック多層基板は、原料組成物であるセラミック粉末中のＢａＯ含有量が多く、十分な耐湿性が得られなかった。他方、サンプルＮｏ．２４のガラスセラミック多層基板は、原料組成物であるガラス粉末中のＢａＯ含有量が少なく、１２ＧＨｚにおけるＱ値が３００を下回ってしまった。 Sample No. The glass ceramic multilayer substrate No. 23 had a large BaO content in the ceramic powder as the raw material composition, and sufficient moisture resistance was not obtained. On the other hand, sample no. The 24 glass-ceramic multilayer substrate had a low BaO content in the glass powder as the raw material composition, and the Q value at 12 GHz was less than 300.
また、サンプルＮｏ．２５のガラスセラミック多層基板は、原料組成物であるセラミック粉末中のＭｇＯ含有量が多く、熱膨張係数αが１２ｐｐｍ／℃を超えてしまった。さらに、サンプルＮｏ．２６のガラスセラミック多層基板は、原料組成物であるセラミック粉末中のＡｌ2Ｏ3含有量が多く、熱膨張係数αが９ｐｐｍ／℃を下回ってしまった。 Sample No. The 25 glass ceramic multilayer substrate had a high MgO content in the ceramic powder as the raw material composition, and the thermal expansion coefficient α exceeded 12 ppm / ° C. Furthermore, sample no. In the glass ceramic multilayer substrate No. 26, the content of Al 2 O 3 in the ceramic powder as the raw material composition was large, and the thermal expansion coefficient α was below 9 ppm / ° C.
１…ガラスセラミック多層基板
２…ガラスセラミック絶縁層
３ａ…一方主面
３ｂ…他方主面
４、５…表面導体パターン
６…内部導体パターン（面内導体）
７…内部導体パターン（ビア導体）
８ａ、８ｂ、８ｃ…表面実装部品
DESCRIPTION OF SYMBOLS 1 ... Glass ceramic multilayer substrate 2 ... Glass ceramic insulating layer 3a ... One main surface 3b ... The other main surface 4, 5 ... Surface conductor pattern 6 ... Internal conductor pattern (in-plane conductor)
7 ... Internal conductor pattern (via conductor)
8a, 8b, 8c ... surface mount components
Claims (4)
酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末を３５〜５０重量％と、
を含み、
さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有する、ガラスセラミック原料組成物。 20-40 wt% of silicon oxide in terms of SiO 2, 30-60 wt% barium oxide in terms of BaO, 5 to 20 wt% of magnesium oxide in terms of MgO, 0 to 10 wt% of zinc oxide calculated as ZnO, oxide 0 to 10 wt% of aluminum in terms of Al 2 O 3, and 50-65 wt% of glass powder containing 0-10 wt% of boron oxide in terms of B 2 O 3,
50-70 wt% of silicon oxide in terms of SiO 2, 10-40 wt% barium oxide in terms of BaO, 0 to 20 wt% of magnesium oxide in terms of MgO, 0 to 15 weight aluminum oxide in terms of Al 2 O 3 35 to 50% by weight of ceramic powder containing
Only including,
Furthermore, when at least one of cerium oxide and titanium oxide is included , the glass ceramic raw material composition contains cerium oxide in a proportion of 5% by weight or less in terms of CeO 2 and titanium oxide in a proportion of 5% by weight or less in terms of TiO 2 , respectively. object.
酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末を３５〜５０重量％と、
を含み、
さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有するガラスセラミック原料組成物を焼成してなり、ＢａＯ・２ＭｇＯ・２ＳｉＯ2を主とする結晶相を析出している、ガラスセラミック焼結体。 20-40 wt% of silicon oxide in terms of SiO 2, 30-60 wt% barium oxide in terms of BaO, 5 to 20 wt% of magnesium oxide in terms of MgO, 0 to 10 wt% of zinc oxide calculated as ZnO, oxide 0 to 10 wt% of aluminum in terms of Al 2 O 3, and 50-65 wt% of glass powder containing 0-10 wt% of boron oxide in terms of B 2 O 3,
50-70 wt% of silicon oxide in terms of SiO 2, 10-40 wt% barium oxide in terms of BaO, 0 to 20 wt% of magnesium oxide in terms of MgO, 0 to 15 weight aluminum oxide in terms of Al 2 O 3 35 to 50% by weight of ceramic powder containing
Only including,
Further, when at least one of cerium oxide and titanium oxide is contained, the glass ceramic raw material composition contains cerium oxide in a proportion of 5% by weight or less in terms of CeO 2 and titanium oxide in a proportion of 5% by weight or less in terms of TiO 2 , respectively . A sintered glass ceramic body in which a crystal phase mainly composed of BaO.2MgO.2SiO 2 is precipitated.
酸化ケイ素をＳｉＯ2換算で５０〜７０重量％、酸化バリウムをＢａＯ換算で１０〜４０重量％、酸化マグネシウムをＭｇＯ換算で０〜２０重量％、酸化アルミニウムをＡｌ2Ｏ3換算で０〜１５重量％含有するセラミック粉末を３５〜５０重量％と、を含み、
さらに、酸化セリウムと酸化チタンの少なくとも一方を含む場合には、それぞれ酸化セリウムをＣｅＯ 2 換算で５重量％以下、酸化チタンをＴｉＯ 2 換算で５重量％以下の割合で含有するガラスセラミック原料組成物を焼成してなり、ＢａＯ・２ＭｇＯ・２ＳｉＯ2を主とする結晶相を析出している、複数のガラスセラミック絶縁層と、
前記複数のガラスセラミック絶縁層の間に設けられるＡｇ系導体パターンと、
を備える、ガラスセラミック多層基板。 20-40 wt% of silicon oxide in terms of SiO 2, 30-60 wt% barium oxide in terms of BaO, 5 to 20 wt% of magnesium oxide in terms of MgO, 0 to 10 wt% of zinc oxide calculated as ZnO, oxide 0 to 10 wt% of aluminum in terms of Al 2 O 3, and 50-65 wt% of glass powder containing 0-10 wt% of boron oxide in terms of B 2 O 3,
50-70 wt% of the oxide of silicon in terms of SiO 2, 10-40 wt% barium oxide in terms of BaO, 0 to 20 wt% of magnesium oxide in terms of MgO, 0 to 15 weight aluminum oxide in terms of Al 2 O 3 % seen including and a 35-50% by weight of ceramic powder containing,
Further, when at least one of cerium oxide and titanium oxide is contained, the glass ceramic raw material composition contains cerium oxide in a proportion of 5% by weight or less in terms of CeO 2 and titanium oxide in a proportion of 5% by weight or less in terms of TiO 2 , respectively . A plurality of glass ceramic insulating layers, wherein a crystal phase mainly composed of BaO · 2MgO · 2SiO 2 is precipitated,
An Ag-based conductor pattern provided between the plurality of glass ceramic insulating layers;
A glass ceramic multilayer substrate comprising:
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