JP7351205B2 - 誘電体組成物および電子部品 - Google Patents
誘電体組成物および電子部品 Download PDFInfo
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- JP7351205B2 JP7351205B2 JP2019224821A JP2019224821A JP7351205B2 JP 7351205 B2 JP7351205 B2 JP 7351205B2 JP 2019224821 A JP2019224821 A JP 2019224821A JP 2019224821 A JP2019224821 A JP 2019224821A JP 7351205 B2 JP7351205 B2 JP 7351205B2
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- 239000000203 mixture Substances 0.000 title claims description 57
- 239000011575 calcium Substances 0.000 claims description 59
- 229910052791 calcium Inorganic materials 0.000 claims description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 30
- 229910052712 strontium Inorganic materials 0.000 claims description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims description 24
- 239000011574 phosphorus Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 16
- 229910007746 Zr—O Inorganic materials 0.000 claims description 5
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 47
- 239000000843 powder Substances 0.000 description 30
- 239000000654 additive Substances 0.000 description 27
- 230000000996 additive effect Effects 0.000 description 25
- 239000003990 capacitor Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
- 238000010304 firing Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000003985 ceramic capacitor Substances 0.000 description 13
- 238000005204 segregation Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229910052735 hafnium Inorganic materials 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 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 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Description
主相と、Ca-Si-P-O偏析相と、を含む誘電体組成物であって、
前記主相はABO3で表される主成分を含み、
前記Aはカルシウムおよびストロンチウムから選ばれる少なくともいずれか1つを含み、
前記Bはジルコニウム、チタン、ハフニウムおよびマンガンから選ばれる少なくともいずれか1つを含み、
前記Ca-Si-P-O偏析相には、少なくともカルシウム、ケイ素およびリンが含まれる。
前記Ca-Si-P-O偏析相に含まれるカルシウム、ストロンチウム、ケイ素およびリンの合計を1モル部としたとき、
前記Ca-Si-P-O偏析相には、
カルシウムが0.24~0.77モル部含まれ、
ストロンチウムが0.00~0.40モル部含まれ、
ケイ素が0.05~0.30モル部含まれ、
リンが0.05~0.40モル部含まれることが好ましい。
本実施形態に係る電子部品の一例としての積層セラミックコンデンサ1が図1に示される。積層セラミックコンデンサ1は、誘電体層2と、内部電極層3と、が交互に積層された構成の素子本体10を有する。この素子本体10の両端部には、素子本体10の内部で交互に配置された内部電極層3と各々導通する一対の外部電極4が形成してある。素子本体10の形状に特に制限はないが、通常、直方体状とされる。また、素子本体10の寸法にも特に制限はなく、用途に応じて適当な寸法とすればよい。
誘電体層2は、後述する本実施形態に係る誘電体組成物から構成されている。
本実施形態では、内部電極層3は、各端部が素子本体10の対向する2端面の表面に交互に露出するように積層してある。
外部電極4に含有される導電材は特に限定されない。たとえばNi、Cu、Sn、Ag、Pd、Pt、Auあるいはこれらの合金、導電性樹脂等公知の導電材を用いればよい。外部電極4の厚さは用途等に応じて適宜決定すればよい。
図2に示すように、本実施形態に係る誘電体層2を構成する誘電体組成物は、主相14の間にCa-Si-P-O偏析相16を含む。
本実施形態の主相14はABO3で表される主成分を含む。なお、主相14の主成分とは、主相100質量部に対して、80~100質量部を占める成分であり、好ましくは、90~100質量部を占める成分である。
図2に示すように、本実施形態に係る誘電体層2を構成する誘電体組成物は、上記の主相14の間に、Ca-Si-P-O偏析相16を含む。Ca-Si-P-O偏析相16には、少なくともカルシウム(Ca)、ケイ素(Si)およびリン(P)が含まれる。これにより、本実施形態の誘電体組成物は、高温多湿の環境下におけるクラックの発生に対して高い抑制効果を発揮することができる。
次に、図1に示す積層セラミックコンデンサ1の製造方法の一例について以下に説明する。
上述した実施形態では、本発明に係る電子部品が積層セラミックコンデンサである場合について説明したが、本発明に係る電子部品は、積層セラミックコンデンサに限定されず、上述した誘電体組成物を有する電子部品であれば何でもよい。
試料番号1~25では、誘電体組成物に含まれる主相の出発原料として、炭酸カルシウム(CaCO3)、炭酸ストロンチウム(SrCO3)、酸化ジルコニウム(ZrO2)、酸化チタン(TiO2)、酸化ハフニウム(HfO2)および炭酸マンガン(MnCO3)の粉末を準備した。焼成後の主相の組成が表1に記載の通りになるように、準備した出発原料を秤量した。
試料番号31では、主相の主成分化合物の仮焼き粉末および第1添加剤の仮焼き粉末の他に第2添加剤の仮焼き粉末を加えて、分散媒を用いてボールミルにより粉砕し、乾燥し、誘電体原料を得た以外は、実験1と同様にしてコンデンサ試料を得た。なお、第2添加剤は焼成後にCa-Zr-O偏析相となる成分である。
試料番号41~44では、第1添加剤の仮焼き粉末のボールミルでの粉砕時間を変えることで円相当径を調整した以外は、実験1と同様にしてコンデンサ試料を得た。
試料番号51~54では、第1添加剤の添加量を変化させた以外は、実験1と同様にしてコンデンサ試料を得た。
10… 素子本体
2… 誘電体層
14… 主相
16… Ca-Si-P-O偏析相
3… 内部電極層
4… 外部電極
Claims (8)
- 主相と、Ca-Si-P-O結晶相と、を含む誘電体組成物であって、
前記主相はABO3で表される主成分を含み、
前記Aはカルシウムを少なくとも含み、前記Bはジルコニウムを少なくとも含み、
前記Ca-Si-P-O結晶相には、少なくともカルシウム、ケイ素およびリンが含まれる誘電体組成物であって、
前記Ca-Si-P-O結晶相に含まれるカルシウム、ストロンチウム、ケイ素およびリンの合計を1モル部としたとき、
前記Ca-Si-P-O結晶相には、
ケイ素が0.05モル部以上含まれ、
リンが0.05モル部以上含まれる誘電体組成物。 - 前記Ca-Si-P-O結晶相に含まれるカルシウム、ストロンチウム、ケイ素およびリンの合計を1モル部としたとき、
前記Ca-Si-P-O結晶相には、
カルシウムが0.24~0.77モル部含まれ、
ストロンチウムが0.00~0.40モル部含まれ、
ケイ素が0.05~0.30モル部含まれ、
リンが0.05~0.40モル部含まれる請求項1に記載の誘電体組成物。 - 前記Ca-Si-P-O結晶相の結晶系は斜方晶系である請求項1または2に記載の誘電体組成物。
- Ca安定化ジルコニアからなるCa-Zr-O系結晶相をさらに含む請求項1~3のいずれかに記載の誘電体組成物。
- 前記Ca安定化ジルコニアは立方晶系である、請求項4に記載の誘電体組成物。
- 前記Ca-Si-P-O結晶相の円相当径は0.02~1μmである請求項1~5のいずれかに記載の誘電体組成物。
- (前記Ca-Si-P-O結晶相の面積/前記主相の面積)×100[%]の式で表される前記Ca-Si-P-O結晶相の面積比率が0.5~10%である請求項1~6のいずれかに記載の誘電体組成物。
- 請求項1~7のいずれかに記載の誘電体組成物を備える電子部品。
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