JP6144757B2 - 多層デバイスの製造方法およびこの方法によって製造される多層デバイス - Google Patents
多層デバイスの製造方法およびこの方法によって製造される多層デバイス Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000010949 copper Substances 0.000 claims description 70
- 229910052802 copper Inorganic materials 0.000 claims description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 239000007772 electrode material Substances 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000005751 Copper oxide Substances 0.000 claims description 18
- 229910000431 copper oxide Inorganic materials 0.000 claims description 18
- 238000009792 diffusion process Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 241001385733 Aesculus indica Species 0.000 claims 1
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- -1 Copper cations Chemical class 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H10N30/508—Piezoelectric or electrostrictive devices having a stacked or multilayer structure adapted for alleviating internal stress, e.g. cracking control layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01G4/12—Ceramic dielectrics
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- H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
- H10N30/053—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by integrally sintering piezoelectric or electrostrictive bodies and electrodes
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/80—Sintered
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
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Description
A)電極材料と、誘電体材料を含むグリーンシートとを準備するステップ。
B)少なくとも酸化銅を含む助剤を準備するステップ。
C)誘電性のグリーンシート,上記の助剤を含む少なくとも1つの薄層,および上記電極材料を含む層が交互に重なって設けられた積層体(1)を形成するステップと、
D)上記の積層体(1)を脱バインダおよび焼結するステップ、
とを備え、
ここで方法ステップD)において、上記の酸化銅が金属銅に還元され、上記の少なくとも1つの薄層が分解される。
方法ステップC)で形成された積層体に関し、「交互に」は、全てのグリーンシートの上に電極材料または助剤からなる薄層が取付けられることを必ずしも意味しない。たとえば、幾つかの圧電性グリーンシートが重なって設けられていてよく、これらの間に電極材料からなる層が存在しなくともよい。
このためこの脱バインダおよび焼結の際に、それぞれのプロセスウィンドウ(Prozessfenster)が調整されて、自動調整される酸素の平衡分圧がPb/PbOとCu2O/Cuの曲線の間になる(PbOおよびCuが同時に存在している)ようにされる(図4参照)。好ましくは、この脱バインダの際の酸素分圧は、600℃でpO2=10−18〜10−13気圧に調整され、200℃でpO2=10−40〜10−35気圧に調整される。焼結は、好ましくは、1010℃の温度でCu2O/CuおよびPb/PbOの平衡曲線の間(図4参照)で行われる。この焼結の際には雰囲気は、好ましくはH2O/N2から成る混合物に設定される。
1つの実施形態によれば、上記の電極材料は銅を含み、好ましくは金属銅または銅合金を含む。
CuO → Cu+0.5O2 あるいは Cu2O → 2Cu+0.5O2
銅カチオンは、金属銅より速く拡散する。添加されたCu成分の酸素部分が大きいほど、脱バインダ処理での拡散は大きくなる。図dの場合においては、酸化銅成分が全く無く、この拡散は全てのほかのCu電極より大きくも小さくもない。
図3bにおいては、この黒化はこの助剤層の両側でそれぞれ2つの隣接する電極層を含むものとなっている。図3aと3bの比較から、黒化が起こる領域が図3bにおいては図3aのほぼ2倍となっていることが分かる。以上より助剤としてCuO(銅の酸化数:2)がCu2Oより好ましいことが分かる。これは2価の銅はより大きな拡散度(Diffusionsgrad)およびより大きな拡散距離(Diffusionslange)を有しているからである。
10 圧電層
20 内部電極
21 脆弱層
25 亀裂
30 外部電極
Claims (11)
- 多層デバイスの製造方法であって、
A)電極材料と、誘電体材料を含むグリーンシートとを準備するステップと、
B)少なくとも酸化銅を含む助剤を準備するステップと、
C)誘電性のグリーンシート,前記助剤を含む少なくとも1つの薄層,および前記電極材料を含む層が交互に重なって設けられた積層体(1)を形成するステップと、
D)前記積層体(1)を脱バインダおよび焼結するステップ、
とを備え、
前記方法ステップC)において、前記助剤を含む少なくとも1つの薄層は、2つの電極材料を含む層に対し平行またはほぼ平行となっており、さらに2つのグリーンシートに接して設けられており、
前記方法ステップD)において、上記の酸化銅が金属銅に還元され、上記の少なくとも1つの薄層が分解されることで、誘電性セラミック層と、前記誘電性セラミックス層の間に内部電極および少なくとも1つの脆弱層とを備えた、多層誘電体デバイスが製造されることを特徴とする方法。 - 前記電極材料および前記助剤は、これらが同じ金属を含み、前記電極材料に存在する当該金属の分量が、前記助剤における当該金属の分量よりも少なくなるように選択されることを特徴とする、請求項1に記載の方法。
- 前記方法ステップD)で、前記酸化銅から銅イオンが、前記電極材料(20)を含む層の少なくとも1つに拡散侵入(hindiffundieren)することを特徴とする、請求項2に記載の方法。
- 前記方法ステップd)において、前記酸化銅が前記金属銅に還元されるように酸素分圧が調整されることを特徴とする、請求項1乃至3のいずれか1項に記載の方法。
- 前記酸化銅の前記銅への還元は、既に前記脱バインダ後に殆ど終了していることを特徴とする、請求項4に記載の方法。
- 前記積層体(1)の薄層の領域での拡散によって、脆弱層(21)が形成されることを特徴とする、請求項5に記載の方法。
- 酸化銅としてCuOまたはCu2Oが用いられることを特徴とする、請求項1乃至6のいずれか1項に記載の方法。
- 前記助剤は、金属銅を全く含まないことを特徴とする、請求項1乃至7のいずれか1項に記載の方法。
- 前記助剤は、1つの成分のみからなることを特徴とする、請求項1乃至8のいずれか1項に記載の方法。
- 前記電極は銅を含むことを特徴とする、請求項1乃至9のいずれか1項に記載の方法。
- 前記誘電体材料は、圧電材料であることを特徴とする、請求項1乃至10のいずれか1項に記載の方法。
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PCT/EP2013/058299 WO2013167368A1 (de) | 2012-05-07 | 2013-04-22 | Verfahren zur herstellung eines vielschichtbauelements und durch das verfahren hergestellte vielschichtbauelement |
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---|---|---|---|---|
JPS62282409A (ja) | 1986-05-30 | 1987-12-08 | 松下電器産業株式会社 | 電圧依存性非直線抵抗器 |
JP2695352B2 (ja) * | 1992-07-27 | 1997-12-24 | 株式会社日立製作所 | 多層セラミック基板の製造装置 |
US5459368A (en) | 1993-08-06 | 1995-10-17 | Matsushita Electric Industrial Co., Ltd. | Surface acoustic wave device mounted module |
JPH08167536A (ja) | 1994-12-14 | 1996-06-25 | Tdk Corp | 銅内部電極積層セラミックコンデンサの製造方法 |
JP3527854B2 (ja) | 1998-09-30 | 2004-05-17 | 京セラ株式会社 | 導電性ペースト組成物及びそれを用いた積層セラミックコンデンサの製造方法、並びに積層セラミックコンデンサ |
JP2002260951A (ja) * | 2000-12-28 | 2002-09-13 | Denso Corp | 積層型誘電素子及びその製造方法,並びに電極用ペースト材料 |
JP2002260950A (ja) * | 2000-12-28 | 2002-09-13 | Denso Corp | 積層型誘電素子の製造方法,並びに電極用ペースト材料 |
JP2002314156A (ja) | 2001-04-12 | 2002-10-25 | Denso Corp | 圧電体素子 |
US7272876B2 (en) * | 2002-11-05 | 2007-09-25 | Nippon Soken, Inc. | Method for fabricating laminate-type dielectric element |
JP4393841B2 (ja) | 2002-11-05 | 2010-01-06 | 株式会社デンソー | 積層型誘電素子及びその製造方法 |
JP4066432B2 (ja) * | 2003-10-31 | 2008-03-26 | Necトーキン株式会社 | 積層型圧電セラミックス素子の製造方法 |
JP2006108546A (ja) | 2004-10-08 | 2006-04-20 | Nec Tokin Corp | 積層型圧電セラミックス素子およびその製造方法 |
WO2007097460A1 (ja) * | 2006-02-27 | 2007-08-30 | Kyocera Corporation | セラミック部材の製造方法、並びにセラミック部材、ガスセンサ素子、燃料電池素子、フィルタ素子、積層型圧電素子、噴射装置、及び燃料噴射システム |
JP4930410B2 (ja) | 2007-02-26 | 2012-05-16 | 株式会社デンソー | 積層型圧電素子 |
WO2009092584A1 (de) | 2008-01-23 | 2009-07-30 | Epcos Ag | Piezoelektrisches vielschichtbauelement |
DE102009043000A1 (de) | 2009-05-29 | 2010-12-02 | Epcos Ag | Piezoelektrisches Vielschichtbauelement |
DE102010020192A1 (de) | 2010-05-11 | 2011-11-17 | Epcos Ag | Piezoelektrisches Vielschichtbauelement |
DE102011109008A1 (de) | 2011-07-29 | 2013-01-31 | Epcos Ag | Verfahren zur Herstellung eines piezoelektrischen Vielschichtbauelements |
-
2012
- 2012-05-07 DE DE102012103994A patent/DE102012103994A1/de not_active Ceased
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2013
- 2013-04-22 US US14/398,422 patent/US11104114B2/en active Active
- 2013-04-22 EP EP13718184.8A patent/EP2847805B1/de active Active
- 2013-04-22 JP JP2015510710A patent/JP6144757B2/ja active Active
- 2013-04-22 WO PCT/EP2013/058299 patent/WO2013167368A1/de active Application Filing
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EP2847805A1 (de) | 2015-03-18 |
JP2015521379A (ja) | 2015-07-27 |
US20150132589A1 (en) | 2015-05-14 |
DE102012103994A1 (de) | 2013-11-21 |
US11104114B2 (en) | 2021-08-31 |
EP2847805B1 (de) | 2017-07-26 |
WO2013167368A1 (de) | 2013-11-14 |
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