JPWO2012063642A1 - 強誘電体薄膜、強誘電体薄膜の製造方法、圧電体素子の製造方法 - Google Patents
強誘電体薄膜、強誘電体薄膜の製造方法、圧電体素子の製造方法 Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000010408 film Substances 0.000 claims abstract description 176
- 239000000758 substrate Substances 0.000 claims abstract description 65
- 239000000654 additive Substances 0.000 claims abstract description 49
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 47
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- 238000013329 compounding Methods 0.000 claims description 23
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
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- 239000002131 composite material Substances 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims 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 38
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 38
- 239000013078 crystal Substances 0.000 description 25
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
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- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 3
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
図4に実施例1の成膜フローを示す。実施例1は、基板がシリコン基板であり、添加物がLaであって、PZTにLaを添加した複合酸化物であるPLZT薄膜を成膜している。また、このLaの配合濃度は、薄膜の厚み方向に向かって濃度が実質的に0の状態から所定濃度まで徐々に増加させる構成としている。
図6に実施例2の成膜フローを示す。実施例2は、基板がシリコン基板であり、添加物がLaであって、PZTにLaを添加した複合酸化物であるPLZT薄膜を成膜している。また、このLaの配合濃度は、薄膜の厚み方向に向かって濃度が実質的に0の層と、濃度が所定濃度(例えば、8%)の層とをそれぞれ所定厚みで順次積層した構成としている。
図8Aは、本実施形態で作製した圧電素子を備えた圧電デバイス20をダイヤフラム(振動板)に応用したときの構成を示す平面図であり、図8Bは、図8AのVIIIB−VIIIB線矢視断面図である。圧電体膜L4は、基板B1の必要な領域に、2次元の千鳥状に配置されている。基板B1において圧電体膜L4の形成領域に対応する領域は、厚さ方向の一部が断面円形で除去された凹部B1aとなっており、基板B1における凹部B1aの上部(凹部B1aの底部側)には、薄い板状の領域B1bが残っている。下部電極層D1および上部電極層D2は、図示しない配線により、外部の制御回路と接続されている。
以上、添加物としてLaを用いたPLZTについて説明したが、本発明は、Laに限らず、圧電特性を発揮可能なその他の添加物を用いることができる。例えば、Aサイトには、Nd等のランタノイド、Sr、またはBiの群から選ばれた少なくとも1種の金属材料を用いることができる。また、Bサイトには、Nb、Ta、W、またはSbの群から選ばれた少なくとも1種の金属材料を用いることができる。また、AサイトとBサイトの両方に添加物が含まれていてもよい。
L1 熱酸化膜
D1 下部電極層
D2 上部電極層
L4 誘電体膜(強誘電体薄膜:圧電体膜)
S3 順次成膜工程
S16 繰り返し成膜工程
10 成膜装置
Claims (20)
- 基体上にペロブスカイト構造の誘電体材料を成膜した強誘電体薄膜であって、
前記誘電体材料は、PZTに、Pb、Zr、及びTi以外の金属材料の添加物を配合した複合酸化物で構成され、前記添加物の配合濃度を、前記基体近くにおいては実質的に0とし、前記薄膜の厚み方向に変化させたことを特徴とする強誘電体薄膜。 - 前記配合濃度は、前記薄膜の厚み方向に向かって濃度が実質的に0の状態から所定濃度まで連続的に増加していることを特徴とする請求項1に記載の強誘電体薄膜。
- 前記配合濃度は、前記薄膜の厚み方向に向かって、前記濃度が実質的に0の層と、前記濃度が所定濃度の層とを、それぞれ所定厚みで交互に繰り返していることを特徴とする請求項1に記載の強誘電体薄膜。
- 前記添加物が、ABO3構成のペロブスカイト構造におけるAサイトに置換される添加物であって、LaやNdを含むランタノイド、および、Sr,または、Biの群から選ばれた少なくとも1種の金属イオンであることを特徴とする請求項1から3のいずれかに記載の強誘電体薄膜。
- 前記添加物が、ABO3構成のペロブスカイト構造におけるBサイトに置換される添加物であって、Nb、Ta、W、または、Sbの群から選ばれた少なくとも1種の金属イオンであることを特徴とする請求項1から4のいずれかに記載の強誘電体薄膜。
- 前記添加物がLaであって、前記Laの配合濃度は、前記薄膜の厚み方向に向かって濃度が実質的に0の状態から所定濃度の8%まで連続的に増加していることを特徴とする請求項2に記載の強誘電体薄膜。
- 前記添加物がLaであって、前記Laの配合濃度は、前記薄膜の厚み方向に向かって、前記濃度が実質的に0の層と、前記濃度が所定濃度の8%の層とを、それぞれ所定厚みで交互に繰り返していることを特徴とする請求項3に記載の強誘電体薄膜。
- 前記薄膜の全厚みを3〜5μmとしたことを特徴とする請求項1から7のいずれかに記載の強誘電体薄膜。
- 基体上にペロブスカイト構造の誘電体材料を成膜した強誘電体薄膜の製造方法であって、前記誘電体材料として、PZTに、Pb、Zr、及びTi以外の金属材料の添加物を配合した複合酸化物を用い、前記添加物の配合濃度を、前記基体近くにおいては実質的に0とし、前記薄膜の厚み方向に変化させて成膜する圧電体膜成膜工程を有することを特徴とする強誘電体薄膜の製造方法。
- 前記圧電体膜成膜工程が、成膜される薄膜の厚み方向に向かって前記添加物の配合濃度が実質的に0の状態から所定濃度まで連続的に増加している圧電体膜を成膜していく成膜工程であることを特徴とする請求項9に記載の強誘電体薄膜の製造方法。
- 前記圧電体膜成膜工程が、成膜される薄膜の厚み方向に向かって、前記添加物の配合濃度が実質的に0の層と、前記濃度が所定濃度の層とをそれぞれ所定厚みで交互に繰り返し順次積層していく繰り返し成膜工程であることを特徴とする請求項9に記載の強誘電体薄膜の製造方法。
- 前記圧電体膜成膜工程が、高周波マグネトロンスパッタリング法により前記基体上に成膜を行うことを特徴とする請求項9から11のいずれかに記載の強誘電体薄膜の製造方法。
- 前記圧電体膜成膜工程が、
PZTで構成される第一ターゲットを第一の高周波電源を介してスパッタリング可能に装着する工程と、
前記添加物で構成される第二ターゲットを第二の高周波電源を介してスパッタリング可能に装着する工程と、
前記第一及び第二の高周波電源の出力を調整することにより、前記添加物の配合濃度を変化させつつ成膜を行う工程とを備えたことを特徴とする請求項12に記載の強誘電体薄膜の製造方法。 - 前記圧電体膜成膜工程が、前記第二の高周波電源の出力を徐々に増加させて、前記濃度が連続的に増加している圧電体膜を成膜していくことを特徴とする請求項13に記載の強誘電体薄膜の製造方法。
- 前記圧電体膜成膜工程が、前記第一及び第二の高周波電源の出力を一定に保持するとともに、第二ターゲットから放出される物質の前記基体上への到達を阻止するシャッタを開閉制御して、前記濃度が実質的に0の層と、前記濃度が所定濃度の層とをそれぞれ所定厚みで交互に繰り返し順次積層していくことを特徴とする請求項13に記載の強誘電体薄膜の製造方法。
- 前記添加物がLaであって、前記Laの所定濃度は8%であることを特徴とする請求項10または11に記載の強誘電体薄膜の製造方法。
- 圧電素子の製造方法であって、
シリコン基板に熱酸化膜を形成する保護膜形成工程と、
形成された熱酸化膜上に下部電極層を成膜する下部電極形成工程と、
成膜された下部電極層上にペロブスカイト構造の圧電体膜を成膜する工程であって、前記圧電体膜の材料として、PZTに、Pb、Zr及びTi以外の金属材料の添加物を配合した複合酸化物を用い、前記添加物の濃度を、前記下部電極層近くにおいては実質的に0とし、前記薄膜の厚み方向に変化させて成膜する圧電体膜成膜工程と、
成膜された圧電体膜に上部電極層を成膜する上部電極形成工程と、を有することを特徴とする圧電素子の製造方法。 - 前記圧電体膜成膜工程が、成膜される薄膜の厚み方向に向かって前記添加物の配合濃度が実質的に0の状態から所定濃度まで連続的に増加している圧電体膜を成膜していく成膜工程であることを特徴とする請求項17に記載の圧電素子の製造方法。
- 前記圧電体膜成膜工程が、成膜される薄膜の厚み方向に向かって、前記添加物の配合濃度が0の層と、前記添加物の配合濃度が所定濃度の層とをそれぞれ所定厚みで交互に繰り返し順次積層していく繰り返し成膜工程であることを特徴とする請求項17に記載の圧電素子の製造方法。
- 前記添加物がLaであって、前記Laの所定濃度は8%であることを特徴とする請求項18または19に記載の圧電素子の製造方法。
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