JP2007073598A - 複合酸化物積層体、複合酸化物積層体の製造方法、デバイス - Google Patents
複合酸化物積層体、複合酸化物積層体の製造方法、デバイス Download PDFInfo
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- JP2007073598A JP2007073598A JP2005256416A JP2005256416A JP2007073598A JP 2007073598 A JP2007073598 A JP 2007073598A JP 2005256416 A JP2005256416 A JP 2005256416A JP 2005256416 A JP2005256416 A JP 2005256416A JP 2007073598 A JP2007073598 A JP 2007073598A
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- complex oxide
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- H—ELECTRICITY
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Abstract
【解決手段】 基板20と、前記基板20の上方に形成され、一般式ABO3で表される第1複合酸化物層24と、前記第1複合酸化物層24の上方に形成され、一般式AB1−xCxO3で表される第2複合酸化物層26と、を含み、A元素は、少なくともPbからなり、B元素は、Zr、Ti、V、WおよびHfの少なくとも一つからなり、C元素は、NbおよびTaの少なくとも一つからなる。
【選択図】 図1
Description
基板と、
前記基板の上方に形成され、一般式ABO3で表される第1複合酸化物層と、
前記第1複合酸化物層の上方に形成され、一般式AB1−xCxO3で表される第2複合酸化物層と、を含み、
A元素は、少なくともPbからなり、
B元素は、Zr、Ti、V、WおよびHfの少なくとも一つからなり、
C元素は、NbおよびTaの少なくとも一つからなる。
前記B元素は、ZrおよびTiであり、
前記C元素は、Nbであることができる。
前記第2複合酸化物層は、0.1≦x≦0.3の範囲でNbを含む複合酸化物からなることができる。
さらに、前記第2複合酸化物層は、0.5モル%以上のSiおよびGeの少なくとも一方を含むことができる。
前記第2複合酸化物層は、前記第1複合酸化物層より膜厚が小さいことができる。
前記基板は、電極層を有することができる。
前記第1複合酸化物層の下方に、該第1複合酸化物層の結晶配向性を制御するためのバッファ層を有することができる。
基板の上方に、一般式ABO3で表される第1複合酸化物層を形成する工程と、
前記第1複合酸化物層の上方に、一般式AB1−xCxO3で表される第2複合酸化物層を形成する工程と、を含み、
A元素は、少なくともPbからなり、
B元素は、Zr、Ti、V、WおよびHfの少なくとも一つからなり、
C元素は、NbおよびTaの少なくとも一つからなる。
前記第2複合酸化物層は、一般式AB1−xCxO3で表される絶縁性複合酸化物を形成するための前駆体を含む前駆体組成物を塗布した後、熱処理を行うことにより形成されることができる。
前記前駆体組成物は、少なくとも前記B元素および前記C元素を含み、かつ一部にエステル結合を有する前駆体を含むことができる。
前記前駆体は、さらに、SiおよびGeの少なくとも一方を含むことができる。
図1は、本実施形態にかかる複合酸化物積層体100を模式的に示す断面図である。
本発明の実施形態にかかる複合酸化物積層体の製造方法は、少なくとも以下の工程を有する。
まず、基板20の上に、一般式ABO3で表される第1複合酸化物層22を形成する。図1に示す例では、A元素がPbからなり、B元素がZrおよびTiからなるPb(Zr,Ti)O3であることができる。
第2複合酸化物層26は、例えば、一般式AB1−xCxO3で表される絶縁性複合酸化物を形成するための前駆体を含む前駆体組成物を塗布した後、熱処理を行うことにより形成することができる。
本製造方法で用いられる前駆体組成物は、第2複合酸化物層26の形成に用いられる。ここで、第2複合酸化物層は、一般式AB1−xCxO3で示され、A元素は少なくともPbからなり、B元素はZr、Ti、V、WおよびHfの少なくとも一つからなり、C元素は、NbおよびTaの少なくとも一つからなることができる。さらに、第2複合酸化物層26は、一般式AB1−xCxO3で示され、A元素がPbからなり、B元素がZrおよびTiからなり、C元素がNbからなることができる。そして、本実施形態では、前駆体は、少なくともB元素およびC元素を含み、かつ一部にエステル結合を有する。
プロパノール(プロピルアルコール)として、1−プロパノール(沸点97.4℃)、2−プロパノール(沸点82.7℃)、
ブタノール(ブチルアルコール)として、1−ブタノール(沸点117℃)、2−ブタノール(沸点100℃)、2−メチル−1−プロパノール(沸点108℃)、2−メチル−2−プロパノール(融点25.4℃,沸点83℃)、
ペンタノール(アミルアルコール)として、1−ペンタノール(沸点137℃)、3−メチル−1−ブタノール(沸点131℃)、2−メチル−1−ブタノール(沸点128℃)、2,2ジメチル−1−プロパノール(沸点113℃)、2−ペンタノール(沸点119℃)、3−メチル−2−ブタノール(沸点112.5℃)、3−ペンタノール(沸点117℃)、2−メチル−2−ブタノール(沸点102℃)、
多価アルコール類;
エチレングリコール(融点−11.5℃,沸点197.5℃)、グリセリン(融点17℃,沸点290℃)、
前駆体組成物は、後に詳述するように、前駆体がポリカルボン酸と金属アルコキシドとのエステル化によるエステル結合を有していて可逆的反応が可能なため、高分子化された前駆体を分解して金属アルコキシドとすることができる。そのため、この金属アルコキシドを前駆体原料として再利用することができる。
本実施形態で用いられる前駆体組成物の製造方法は、少なくとも前記B元素および前記C元素を含むゾルゲル原料であって、金属アルコキシドの加水分解・縮合物を含むゾルゲル原料と、ポリカルボン酸またはポリカルボン酸エステルと、有機溶媒とを混合し、前記ポリカルボン酸または前記ポリカルボン酸エステルに由来するポリカルボン酸と金属アルコキシドとのエステル化によるエステル結合を有する前駆体を形成することを含む。
本実施形態にかかる複合酸化物積層体をキャパシタとして用いる場合には、第2複合酸化物層26上に、上部電極を形成する。図1に示す例では、第2複合酸化物層26上に第3電極層28を形成し、当該第3電極層28上に第4電極層30を形成する。第3電極層28は、第2複合酸化物層28と同じペロブスカイト型構造を有する導電性複合酸化物層からなることができる。第3電極層28としては、例えば第2電極層23と同様にLaNiO3を用いることができる。第4電極層30としては、例えば第1電極層22と同様にPtなどの白金族金属を用いることができる。第3電極層28は、レーザーアブレーション法、スパッタ法、CVD法などによって形成することができる。第4電極層30は、スパッタ法などによって形成することができる。
本実施形態にかかる複合酸化物積層体をキャパシタとして用いる場合には、第1、第2複合酸化物層24,26および第3、第4電極層28,30を公知のリソグラフィーおよびエッチングによってパターニングする。
以下、本発明の実施例について述べるが、本発明はこれらに限定されない。
実施例1にかかる複合酸化物積層体は、以下のようにして得た。実施例1では、第1複合酸化物層としてPZT層を用い、第2複合酸化物層としてPZTN層を用いた。なお、部材の参照番号は図1に示すものと同じである。
まず、シリコン基板(基材)21上に、90nmのPt層(第1電極層)22、および60nmのLaNiO3層(第2電極層)23が順次形成された基板20を準備した。Pt層およびLaNiO3層は、それぞれスパッタ法で形成されたものである。
次いで、前駆体組成物を調整し、これを用いてPZTNからなる第2複合酸化物層(以下、「PZTN層」ともいう)26を形成した。この工程で用いた前駆体組成物は、以下の方法で得た。
ついで、第2複合酸化物層(PZTN層)24上に、スパッタ法にて、60nmのLaNiO3層(第3電極層)28と、50nmのPt層(第4電極層)30を順次形成した。さらに、公知のリソグラフィーおよびドライエッチングによって、第4電極層30,第3電極層28、第2複合酸化物層26および第1複合酸化物層24をパターニングし、キャパシタを形成した。ついで、トリメチルシランを用いたCVD法によって保護層(酸化シリコン層)32を形成した。
第2複合酸化物層26を形成しない他は、実施例1と同様にして比較用キャパシタを得た。この比較用キャパシタについて、ヒステリシスを求めたところ、図7(B)の結果が得られた。図7(B)から、比較用キャパシタでは、ある電圧でヒステリシス特性が得られないことが確認された。
本発明のデバイスは、本発明の複合酸化物積層体を有する部品、およびこの部品を有する電子機器を含む。以下に、本発明のデバイスの例を記載する。
次に、本発明の複合酸化物積層体を含む半導体素子について説明する。本実施形態では、半導体素子の一例である強誘電体キャパシタを含む強誘電体メモリ装置を例に挙げて説明する。
次に、本発明の複合酸化物積層体を圧電素子に適用した例について説明する。
次に、上述の圧電素子が圧電アクチュエータとして機能しているインクジェット式記録ヘッドおよびこのインクジェット式記録ヘッドを有するインクジェットプリンタについて説明する。図13は、本実施形態に係るインクジェット式記録ヘッドの概略構成を示す側断面図であり、図14は、このインクジェット式記録ヘッドの分解斜視図であり、通常使用される状態とは上下逆に示したものである。なお、図15には、本実施形態に係るインクジェット式記録ヘッドを有するインクジェットプリンタ700を示す。
次に、本発明の複合酸化物積層体を適用した表面弾性波素子の一例について、図面を参照しながら説明する。
次に、本発明の複合酸化物積層体を適用した周波数フィルタの一例について、図面を参照しながら説明する。図17は、本実施形態の周波数フィルタを模式的に示す図である。
次に、本発明の複合酸化物積層体を適用した発振器の一例について、図面を参照しながら説明する。図18は、本実施形態の発振器を模式的に示す図である。
Claims (12)
- 基板と、
前記基板の上方に形成され、一般式ABO3で表される第1複合酸化物層と、
前記第1複合酸化物層の上方に形成され、一般式AB1−xCxO3で表される第2複合酸化物層と、を含み、
A元素は、少なくともPbからなり、
B元素は、Zr、Ti、V、WおよびHfの少なくとも一つからなり、
C元素は、NbおよびTaの少なくとも一つからなる、複合酸化物積層体。 - 請求項1において、
前記B元素は、ZrおよびTiであり、
前記C元素は、Nbである、複合酸化物積層体。 - 請求項2において、
前記第2複合酸化物層は、0.1≦x≦0.3の範囲でNbを含む複合酸化物からなる、複合酸化物積層体。 - 請求項1ないし3のいずれかにおいて、
さらに、前記第2複合酸化物層は、0.5モル%以上のSiおよびGeの少なくとも一方を含む、複合酸化物積層体。 - 請求項1ないし4のいずれかにおいて、
前記第2複合酸化物層は、前記第1複合酸化物層より膜厚が小さい、複合酸化物積層体。 - 請求項1ないし5のいずれかにおいて、
前記基板は、電極層を有する、複合酸化物積層体。 - 請求項1ないし6のいずれかにおいて、
前記第1複合酸化物層の下方に、該第1複合酸化物層の結晶配向性を制御するためのバッファ層を有する、複合酸化物積層体。 - 基板の上方に、一般式ABO3で表される第1複合酸化物層を形成する工程と、
前記第1複合酸化物層の上方に、一般式AB1−xCxO3で表される第2複合酸化物層を形成する工程と、を含み、
A元素は、少なくともPbからなり、
B元素は、Zr、Ti、V、WおよびHfの少なくとも一つからなり、
C元素は、NbおよびTaの少なくとも一つからなる、複合酸化物積層体の製造方法。 - 請求項8において、
前記第2複合酸化物層は、一般式AB1−xCxO3で表される絶縁性複合酸化物を形成するための前駆体を含む前駆体組成物を塗布した後、熱処理を行うことにより形成される、複合酸化物積層体の製造方法。 - 請求項9において、
前記前駆体組成物は、少なくとも前記B元素および前記C元素を含み、かつ一部にエステル結合を有する前駆体を含む、複合酸化物積層体の製造方法。 - 請求項9および10のいずれかにおいて、
前記前駆体は、さらに、SiおよびGeの少なくとも一方を含む、複合酸化物積層体の製造方法。 - 請求項1ないし7のいずれかに記載の複合酸化物積層体を含む、デバイス。
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US11/514,074 US20070054038A1 (en) | 2005-09-05 | 2006-08-31 | Complex oxide laminate, method of manufacturing complex oxide laminate, and device |
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KR100830013B1 (ko) | 2008-05-15 |
EP1760770A3 (en) | 2008-07-16 |
TW200746388A (en) | 2007-12-16 |
CN1929038A (zh) | 2007-03-14 |
KR20070026258A (ko) | 2007-03-08 |
CN1929038B (zh) | 2010-08-04 |
US20070054038A1 (en) | 2007-03-08 |
EP1760770A2 (en) | 2007-03-07 |
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DE602006017480D1 (de) | 2010-11-25 |
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