JP7333147B2 - 誘電率段階調整可能な低温共焼結誘電体材料及びその製造方法 - Google Patents
誘電率段階調整可能な低温共焼結誘電体材料及びその製造方法 Download PDFInfo
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- JP7333147B2 JP7333147B2 JP2021529074A JP2021529074A JP7333147B2 JP 7333147 B2 JP7333147 B2 JP 7333147B2 JP 2021529074 A JP2021529074 A JP 2021529074A JP 2021529074 A JP2021529074 A JP 2021529074A JP 7333147 B2 JP7333147 B2 JP 7333147B2
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- 239000003989 dielectric material Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 34
- 239000010703 silicon Substances 0.000 claims description 34
- 239000000945 filler Substances 0.000 claims description 33
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Description
ジルコニア主相とシリコン系非結晶相充填材からなる低温共焼結誘電体材料は、誘電率調整可能性が向上し、7~12の範囲内の誘電率の調整を達成することができる。
好ましくは、前記低温共焼結誘電体材料が、重量百分率で、ZrO2 40%~65%、SiO2 27.03%~46.33%、Na2O 0.27%~0.46%、K2O 1.23%~2.11%、CaO 0.73%~1.26%、及びB2O3 5.73%~9.83%を含む。この材料系は、類似する焼結特性を有し、共焼結の際にクラックや反り等の欠損を避けることができる。
好ましくは、前記ジルコニア主相が、結晶状態又は非結晶状態である。単斜晶ZrO2(~20)と非結晶ZrO2(~22)の誘電率が近いため、いずれか一方又は両方を選択しても、7~12の範囲内の誘電率の調整を達成することができる。
好ましくは、前記シリコン系非結晶相充填材が、ガラス又は非結晶相の混合物である。シリコン系非結晶相を選択すると、高温融解過程を経つ必要がなく、B2O3の揮発を避けることができる。
好ましくは、前記シリコン系非結晶相充填材において、NaとKとの原子比が、Na/K=1:2~4である。上記比率によって、誘電損失を低減することができる。
好ましくは、重量百分率で、前記シリコン系非結晶相充填材におけるAl元素の含有量が≦0.01%である。
好ましくは、前記ZrO2の粒子径が、0.5μm~10μmである。ZrO2の粒子径の範囲内の比表面積が適切となり、この配合で誘電率段階調整可能な低温共焼結誘電体材料を製造することができる。より好ましくは、前記ZrO2の粒子径が、1μm~5μmである。
前記シリコン系非結晶相充填材は、各成分を混合することにより製造されてもよく、湿式化学法により製造されてもよい。好ましくは、前記シリコン系非結晶相充填材の製造方法は、
オルトケイ酸エチルをアルコールと脱イオン水との混合溶液に溶解する工程S1と、
溶液のpHを1~3に調整する工程S2と、
ガラス粉末の元素に対応する塩を加えて、60~80℃で加熱しながら均一に撹拌する工程S3と、
溶液のpHを6~8に調整してゲル化させ、ゲルを乾燥して600~750℃で焼成し、前記ガラス粉を得る工程S4と、
を含む。
前記シリコン系非結晶相充填材の製造方法におけるシリコン以外のその他の元素に対応する塩として、好ましくは、溶解可能な塩であり、Na、K、Ca、Bの硝酸塩、酢酸塩等であってもよい。
好ましくは、工程S1において、前記オルトケイ酸エチルとアルコールと脱イオン水の体積比は、1:5~15:1である。
本発明に係る低温共焼結誘電体材料の製造方法の一実施例として、本実施例における低温共焼結誘電体材料の製造方法は、以下の工程を含む。
9.3mLのオルトケイ酸エチルを、アルコール(100mL)と脱イオン水(9.3mL)との混合溶液に溶解し、加水分解を促進するために、硝酸を加えて溶液のpHが1程度となるように調整して撹拌し、溶液が清澄となった後、NaNO3 0.07g、KNO3 0.24g、Ca(NO3)2・4H2O 0.28g及びHBO3溶液 0.92gを添加し、急激に撹拌しながら75℃で加熱し、その後、アンモニア水を加えてpHが7程度となるように調整してゲル化させ、得られたゲルを乾燥させた後に、700℃で2時間焼成し、シリコン系非結晶相充填材を得た。最後に、49.81%のZrO2(粒子径5μm)と50.19%のシリコン系非結晶相充填材をはかりとり、ボールミルで上記材料を18時間混合して、干燥後、7MPaでドライプレスによりシート状に成形させ、そして、850℃で焼結し、前記低温共焼結セラミック材料を得た。
本発明に係る低温共焼結誘電体材料の製造方法の一実施例として、本実施例における低温共焼結誘電体材料の製造方法は、以下の工程を含む。
9.3mLのオルトケイ酸エチルを、アルコール(93mL)と脱イオン水(9.3mL)との混合溶液に溶解し、加水分解を促進するために、硝酸を加えて溶液のpHが1程度となるように調整して撹拌し、溶液が清澄となった後、NaNO3 0.07g、KNO3 0.24g、Ca(NO3)2・4H2O 0.28g及びHBO3溶液 0.92gを添加し、急激に撹拌しながら80℃で加熱し、その後、アンモニア水を加えてpHが7程度となるように調整してゲル化させ、得られたゲルを乾燥させた後に、700℃で2時間焼成し、シリコン系非結晶相充填材を得た。最後に、55%のZrO2(粒子径5μm)と45%のシリコン系非結晶相充填材をはかりとり、ボールミルで上記材料を15時間混合して、干燥後、7MPaでドライプレスによりシート状に成形させ、そして、850℃で焼結し、前記低温共焼結セラミック材料を得た。
本実施例で製造された低温共焼結誘電体材料の誘電性能は、図1に示すように、誘電率が10.48@1MHzであり、誘電損失が0.0011@1MHzである。本実施例における低温共焼結誘電体材料は、銀電極と共焼結した後にも結合が緊密であり、クラックや反り等の現象が発生することがない。
本発明に係る低温共焼結誘電体材料の製造方法の一実施例として、本実施例における低温共焼結誘電体材料の製造方法は、以下の工程を含む。
9.3mLのオルトケイ酸エチルを、アルコール(100mL)と脱イオン水(9.3mL)との混合溶液に溶解し、加水分解を促進するために、硝酸を加えて溶液のpHが1程度となるように調整して撹拌し、溶液が清澄となった後、NaNO3 0.07g、KNO3 0.24g、Ca(NO3)2・4H2O 0.28g及びHBO3溶液 0.92gを添加し、急激に撹拌しながら60℃で加熱し、その後、アンモニア水を加えてpHが7程度となるように調整してゲル化させ、得られたゲルを乾燥させた後に、700℃で2時間焼成し、シリコン系非結晶相充填材を得た。最後に、60%のZrO2(粒子径5μm)と40%のシリコン系非結晶相充填材をはかりとり、ボールミルで上記材料を16時間混合して、干燥後、7MPaでドライプレスによりシート状に成形させ、そして、850℃で焼結し、前記低温共焼結セラミック材料を得た。
本実施例で製造された低温共焼結誘電体材料の誘電性能は、図1に示すように、誘電率が11.11@1MHzであり、誘電損失が0.0006@1MHzである。
当該成分と銀電極との共焼結の際の相容性を検証するため、5%のポリビニルブチラール(PVB)によりボールミル処理後のジルコニアとガラスとの混合粉末に対して造粒処理を行い、その後、7MPaでドライプレスによりシート状に成形させ、さらに、その表面に銀電極を塗布して形成し、最後に、850℃で焼結した。図2において、(a)は、銀電極との生地シートを共焼結した後の断面のSEM図であり、この図に示すように、銀電極とセラミックとの結合が緊密であり、層分離やクラック現象などが発生することなく、 (b)は、銀の含有量が銀電極とセラミックとの界面で急激に低下することを示しており、焼結過程において拡散がなかったことがわかる。
本発明に係る低温共焼結誘電体材料の製造方法の一実施例として、本実施例における低温共焼結誘電体材料の製造方法は、以下の工程を含む。
9.3mLのオルトケイ酸エチルを、アルコール(100mL)と脱イオン水(9.3mL)との混合溶液に溶解し、加水分解を促進するために、硝酸を加えて溶液のpHが1程度となるように調整して撹拌し、溶液が清澄となった後、NaNO3 0.07g、KNO3 0.24g、Ca(NO3)2・4H2O 0.28g及びHBO3溶液 0.92gを添加し、急激に撹拌しながら60℃で加熱し、その後、アンモニア水を加えてpHが7程度となるように調整してゲル化させ、得られたゲルを乾燥させた後に、700℃で2時間焼成し、シリコン系非結晶相充填材を得た。最後に、65%のZrO2(粒子径5μm)と35%のシリコン系非結晶相充填材をはかりとり、ボールミルで上記材料を15時間混合して、干燥後、7MPaでドライプレスによりシート状に成形させ、そして、850℃で焼結し、前記低温共焼結セラミック材料を得た。
Claims (8)
- ジルコニア主相とシリコン系非結晶相充填材を含み、前記ジルコニア主相とシリコン系非結晶相充填材との重量比が、ジルコニア主相:シリコン系非結晶相充填材=40~65:35~60であり、重量百分率で、前記シリコン系非結晶相充填材におけるSiO2の含有量は≧50%であり、
重量百分率で、ZrO2 40%~65%、SiO2 27.03%~46.33%、Na2O 0.27%~0.46%、K2O 1.23%~2.11%、CaO 0.73%~1.26%、及びB2O3 5.73%~9.83%を含む
ことを特徴とする、誘電率段階調整可能な低温共焼結誘電体材料。 - 前記ジルコニア主相は、結晶状態又は非結晶状態であることを特徴とする、請求項1に記載の誘電率段階調整可能な低温共焼結誘電体材料。
- 前記シリコン系非結晶相充填材は、ガラス又は非結晶相の混合物であることを特徴とする、請求項1に記載の誘電率段階調整可能な低温共焼結誘電体材料。
- 前記シリコン系非結晶相充填材において、NaとKとの原子比が、Na/K=1:2~4であることを特徴とする、請求項1に記載の誘電率段階調整可能な低温共焼結誘電体材料。
- 重量百分率で、前記シリコン系非結晶相充填材におけるAl元素の含有量は≦0.01%であることを特徴とする、請求項1に記載の誘電率段階調整可能な低温共焼結誘電体材料。
- 前記ZrO2の粒子径が、0.5μm~10μmであり、好ましくは、前記ZrO2の粒子径が、1μm~5μmであることを特徴とする、請求項1に記載の誘電率段階調整可能な低温共焼結誘電体材料。
- 請求項1~6のいずれか一項に記載の誘電率段階調整可能な低温共焼結誘電体材料の製造方法であって、
オルトケイ酸エチルをアルコールと脱イオン水との混合溶液に溶解する工程S1と、
溶液のpHを1~3に調整する工程S2と、
シリコン系非結晶相充填材の元素に対応する塩を加えて、60~80℃で加熱しながら均一に撹拌する工程S3と、
溶液のpHを6~8に調整してゲル化させ、ゲルを乾燥して600~750℃で焼成し、前記シリコン系非結晶相充填材を得る工程S4と、
シリコン系非結晶相充填材とジルコニア主相を比率によってボールミルで6~24時間混合し、その後、800~900℃で焼結して、前記誘電率段階調整可能な低温共焼結セラミック材料を得る工程S5を含むことを特徴とする、製造方法。 - 工程S1において、前記オルトケイ酸エチルとアルコールと脱イオン水の体積比は、1:5~15:1であることを特徴とする、請求項7に記載の誘電率段階調整可能な低温共焼結誘電体材料の製造方法。
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