JP7378133B2 - Flexible ceramic element and its manufacturing method - Google Patents
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- 239000000919 ceramic Substances 0.000 title claims description 108
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000010410 layer Substances 0.000 claims description 92
- 239000000758 substrate Substances 0.000 claims description 75
- 239000012790 adhesive layer Substances 0.000 claims description 23
- 230000037303 wrinkles Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 239000010408 film Substances 0.000 description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000004549 pulsed laser deposition Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 240000004050 Pentaglottis sempervirens Species 0.000 description 3
- 235000004522 Pentaglottis sempervirens Nutrition 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910004121 SrRuO Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
特許法第３０条第２項適用 平成３０年９月１９日名古屋国際会議場において開催された第７９回応用物理学会秋季学術講演会で発表Application of Article 30, Paragraph 2 of the Patent Act Presented at the 79th Japan Society of Applied Physics Autumn Academic Conference held at the Nagoya International Conference Center on September 19, 2018
本発明は、フレキシブルなセラミックス素子に関するものであり、特にペロブスカイト構造を有するセラミックスをフレキシブルな素子として提供する。 The present invention relates to a flexible ceramic element, and particularly provides a ceramic having a perovskite structure as a flexible element.
電子機器の小型化に伴い、セラミックス素子も小型化が要求されている。従来セラミックス素子はガラスやシリコン基板といった硬度の高い基板上に薄膜形成されていた。しかし、電子機器のウェアラブル化の製品化の開発が進められており、セラミックス素子もフレキシブルな形態の要求がある。 As electronic devices become smaller, ceramic elements are also required to be smaller. Conventionally, ceramic elements have been formed as thin films on hard substrates such as glass or silicon substrates. However, the development of commercialization of wearable electronic devices is progressing, and there is a demand for flexible ceramic elements.
しかし、セラミックス膜の形成には、基板を高温に加熱する必要があるため、耐熱性の低いフレキシブルな基板（例えばプラスチックフィルム）上へのセラミックス膜の形成は容易でなかった。 However, since forming a ceramic film requires heating the substrate to a high temperature, it has not been easy to form a ceramic film on a flexible substrate (for example, a plastic film) with low heat resistance.
特許文献１には、圧電セラミックス粉末と、ポリテトラフルオロエチレンとエラストマーで構成されたフレキシブルな圧電素子が開示されている。一方、特許文献２には、結晶シリコン基板を陽極化成して多孔質層を形成し、この多孔質層上にエピタキシャル成長法により薄膜結晶を成長させる。レーザービームにより成長結晶表面から多孔質層に至る開口部を設け、この開口部を通して多孔質層を選択エッチングして薄膜結晶を基板から分離する。分離した薄膜結晶を他の支持基板に転写して太陽電池を形成する。 Patent Document 1 discloses a flexible piezoelectric element made of piezoelectric ceramic powder, polytetrafluoroethylene, and an elastomer. On the other hand, in Patent Document 2, a crystalline silicon substrate is anodized to form a porous layer, and a thin film crystal is grown on this porous layer by an epitaxial growth method. An opening is created from the surface of the growing crystal to the porous layer using a laser beam, and the porous layer is selectively etched through the opening to separate the thin film crystal from the substrate. The separated thin film crystal is transferred to another supporting substrate to form a solar cell.
また、非特許文献１には、高温に耐えるＭｇＯ基板上に一度ペロブスカイト構造のセラミックス膜を形成し、それをプラスチックフィルムに接着した後、ＭｇＯ基板を溶解することで、フレキシブルなフィルム基板上に形成したセラミックス素子が開示されている。しかし、この方法では、ＭｇＯ基板を溶解した後、プラスチックフィルム上のセラミックス膜が剥離したり、破損するといった課題があった。 In addition, Non-Patent Document 1 describes that a ceramic film with a perovskite structure is once formed on an MgO substrate that can withstand high temperatures, and then a ceramic film with a perovskite structure is bonded to a plastic film, and then the MgO substrate is melted to form a ceramic film on a flexible film substrate. A ceramic element is disclosed. However, this method has a problem in that the ceramic film on the plastic film peels off or is damaged after the MgO substrate is melted.
特許文献１のように、セラミックス粉末に樹脂を混ぜ、素子の特性を得ようとすると、フレキシブル性は獲得できるものの、素子としての特性は、バルク材と比較すると低下してしまうという課題があった。 As in Patent Document 1, when trying to obtain device characteristics by mixing resin with ceramic powder, flexibility could be obtained, but the device characteristics were degraded compared to bulk materials. .
特許文献２は、セラミックス膜を予め別基板上に形成しておき、基板からセラミックス膜を剥離し、セラミックス膜を他の基板に転写する。したがって、素子を作製する際にセラミックス膜を作製した基板とは別の基板にセラミックス膜が転写される。このような構成にすると、セラミックス膜の作製時に必要な温度処理を耐熱性のある基板上で行うことができ、フレキシブルな基板上にもセラミックス膜を形成することができる。 In Patent Document 2, a ceramic film is formed on a separate substrate in advance, the ceramic film is peeled off from the substrate, and the ceramic film is transferred to another substrate. Therefore, when producing an element, the ceramic film is transferred to a substrate different from the substrate on which the ceramic film was produced. With such a configuration, the temperature treatment necessary for producing the ceramic film can be performed on a heat-resistant substrate, and the ceramic film can also be formed on a flexible substrate.
また、非特許文献１は、特許文献２をさらに推し進めたもので、ＭｇＯ基板上で作製した膜をフレキシブル基板に転写する際に、セラミックス膜がフリーになる工程がない。したがって、非常に薄いセラミックス膜のフレキシブル素子を得ることができる。しかし、非特許文献１の方法では、ＭｇＯ基板を溶解した後、フレキシブル基板上のセラミックス膜が剥離したり、破損するといった課題があった。 Furthermore, Non-Patent Document 1 is a further development of Patent Document 2, and there is no step in which the ceramic film becomes free when transferring the film produced on the MgO substrate to the flexible substrate. Therefore, a flexible element with a very thin ceramic film can be obtained. However, the method disclosed in Non-Patent Document 1 has a problem in that the ceramic film on the flexible substrate peels off or is damaged after melting the MgO substrate.
本発明は上記課題に鑑みて想到されたものであり、セラミックス膜を作製する基板からフレキシブル基板に転写してもセラミックス膜が剥離、破損することのないフレキシブルセラミックス素子を提供するものである。 The present invention was conceived in view of the above problems, and provides a flexible ceramic element in which a ceramic film is not peeled off or damaged even when transferred from a substrate on which a ceramic film is fabricated to a flexible substrate.
具体的に本発明に係るフレキシブルセラミックス素子は、
フレキシブル基板と、
前記フレキシブル基板上面に形成された接着層と、
前記接着層上面に形成された緩衝層と、
前記緩衝層上面に形成されたセラミックス層を有し、
前記セラミックス層には、ピッチが１０μｍ～１００μｍで高さが１μｍ～５０μｍの前記セラミックス層の皺から成る皺構造を有することを特徴とする。
Specifically, the flexible ceramic element according to the present invention includes:
a flexible substrate,
an adhesive layer formed on the top surface of the flexible substrate;
a buffer layer formed on the top surface of the adhesive layer;
a ceramic layer formed on the upper surface of the buffer layer ;
The ceramic layer is characterized in that it has a wrinkle structure consisting of wrinkles of the ceramic layer with a pitch of 10 μm to 100 μm and a height of 1 μm to 50 μm .
また、本発明に係るフレキシブルセラミックス素子の製造方法は、
製造基板の処理面にセラミックス層を形成する工程と、
前記セラミックス層の上面に緩衝層を形成する工程と、
前記緩衝層の上面に接着層を形成する工程と、
前記接着層の上面にフレキシブル基板を配置する工程と、
前記製造基板を除去し、ピッチが１０μｍ～１００μｍで高さが１μｍ～５０μｍの前記セラミックス層の皺から成る皺構造を付与する工程を有することを特徴とする。
Furthermore, the method for manufacturing a flexible ceramic element according to the present invention includes:
a step of forming a ceramic layer on the treated surface of the manufacturing substrate;
forming a buffer layer on the top surface of the ceramic layer;
forming an adhesive layer on the top surface of the buffer layer;
arranging a flexible substrate on the top surface of the adhesive layer;
It is characterized by the step of removing the manufacturing substrate and providing a wrinkled structure consisting of wrinkles of the ceramic layer with a pitch of 10 μm to 100 μm and a height of 1 μm to 50 μm .
本発明に係るフレキシブルセラミックス素子では、緩衝層および接着層が、セラミックス層の破損を防ぐ。そして、緩衝層は、セラミックス膜が、割れを生じることなく皺構造を形成することができるようにする。その結果、セラミックス膜の作製時やフレキシブル基板への転写時に生じる応力を皺構造によって吸収する。そして、素子全体に撓みが付与されたり素子全体を伸縮させても、フレキシブル基板上で割れや剥離、破損といった障害なく、セラミックス膜が維持される。 In the flexible ceramic element according to the present invention, the buffer layer and the adhesive layer prevent damage to the ceramic layer. The buffer layer then allows the ceramic film to form a wrinkled structure without cracking. As a result, the wrinkled structure absorbs stress that occurs during the production of the ceramic film or during transfer to the flexible substrate. Even if the entire element is bent or expanded or contracted, the ceramic film can be maintained on the flexible substrate without problems such as cracking, peeling, or damage.
以下に本発明に係るフレキシブルセラミックス素子について、図面および実施例を用いて説明を行う。なお、以下の説明は本発明の一実施の形態および一実施例についての例示であって、本発明は以下の説明に限定されるものではない。本発明の趣旨を逸脱しない限りにおいて、以下の実施の形態は変更することができる。 The flexible ceramic element according to the present invention will be explained below using drawings and examples. Note that the following description is an illustration of one embodiment and one example of the present invention, and the present invention is not limited to the following description. The following embodiments can be modified without departing from the spirit of the present invention.
本発明に係るフレキシブルセラミックス素子１の構成を図１に示す。なお、以下の説明の都合上、ある層について他の層が接していない側を「上面」とし、他の層が接している側を「下面」と呼ぶ。ある層の両面に他の層がある場合は、特に説明をしない限りフレキシブル基板１６がある側を下面と呼ぶ。 FIG. 1 shows the configuration of a flexible ceramic element 1 according to the present invention. For convenience of explanation below, the side of a certain layer that is not in contact with other layers will be referred to as the "upper surface", and the side that is in contact with other layers will be referred to as the "lower surface". When there are other layers on both sides of a certain layer, the side on which the flexible substrate 16 is located is called the lower surface unless otherwise specified.
図１を参照して、フレキシブルセラミックス素子１は、フレキシブル基板１６と、接着層１４と、緩衝層１２と、セラミックス層１０からなる。さらに、フレキシブル基板１６の上面とセラミックス層１０の上面に他の層があってもよい。また、フレキシブルセラミックス素子１は、セラミックス層１０の上面に皺構造１８を有する。 Referring to FIG. 1, flexible ceramic element 1 includes flexible substrate 16, adhesive layer 14, buffer layer 12, and ceramic layer 10. Furthermore, other layers may be provided on the top surface of the flexible substrate 16 and the top surface of the ceramic layer 10. Furthermore, the flexible ceramic element 1 has a wrinkle structure 18 on the upper surface of the ceramic layer 10.
フレキシブル基板１６は、可撓性を有する基板であれば特に限定されるものではない。例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ポリスチレン、ポリプロピレン、ポリアミド（アラミド）、ポリイミドといった樹脂シート（フィルム材）が好適に利用できる。厚みは数μｍから数百μｍで利用できる。あまり基板厚が厚すぎると、基板自体の可撓性が失われる。 The flexible substrate 16 is not particularly limited as long as it is a flexible substrate. For example, resin sheets (film materials) such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polystyrene, polypropylene, polyamide (aramid), and polyimide can be suitably used. The thickness can be from several μm to several hundred μm. If the substrate thickness is too thick, the flexibility of the substrate itself will be lost.
接着層１４は、粘着性（柔軟性）を有するものが好適に利用できる。フレキシブルセラミックス素子１は、複数層が接着され全体として可撓性を有する。したがって、接着層１４が可撓性を持たない固体になってしまうと、接着層１４自体に割れが生じてしまうからである。接着層１４は数十μｍから数百μｍの厚さにすることができる。 As the adhesive layer 14, one having adhesiveness (flexibility) can be suitably used. The flexible ceramic element 1 has a plurality of layers bonded together and has flexibility as a whole. Therefore, if the adhesive layer 14 becomes a solid without flexibility, cracks will occur in the adhesive layer 14 itself. The adhesive layer 14 can have a thickness of several tens of micrometers to several hundred micrometers.
緩衝層１２は、白金系の金属膜が好適に利用できる。より具体的には、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）である。これらの元素が好適な理由は、現在のところ明確ではない。しかしこれらの元素は、セラミックス、特にペロブスカイト構造に対して親和性が高く、薄膜時の膜強度が高い。その結果、セラミックス層１０が機械的に変形しても、セラミックス層１０の割れや破損を防止すると考えられる。緩衝層１２の厚みは十数ｎｍ～数十ｎｍが好適である。特にセラミックス層１０の厚みの３～１０％程度の厚みが望ましい。 As the buffer layer 12, a platinum-based metal film can be suitably used. More specifically, they are ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). The reason why these elements are preferable is not clear at present. However, these elements have a high affinity for ceramics, especially perovskite structures, and have high film strength when thin films are formed. As a result, even if the ceramic layer 10 is mechanically deformed, it is thought that the ceramic layer 10 is prevented from cracking or being damaged. The thickness of the buffer layer 12 is suitably between ten and several nanometers to several tens of nanometers. In particular, a thickness of about 3 to 10% of the thickness of the ceramic layer 10 is desirable.
セラミックス層１０は、特に限定されるものではないが、ペロブスカイト構造を有するものであれば、好適に利用できる。具体的には、チタン酸バリウムＢａＴｉＯ３（ＢＴＯ）、チタン酸ストロンチウムＳｒＴｉＯ３（ＳＴＯ）、ルテニウム酸ストロンチウムＳｒＲｕＯ３（ＳＲＯ）等が挙げられる。これらのセラミックス層１０は、形状変化による発電特性（圧電効果）や、形状変化による抵抗変化（圧抵抗効果）を有する。セラミックス層１０の厚みは２０ｎｍ～８００ｎｍが好適である。厚すぎると、皺構造１８を持てなくなる。 The ceramic layer 10 is not particularly limited, but any material having a perovskite structure can be suitably used. Specific examples include barium titanate BaTiO 3 (BTO), strontium titanate SrTiO 3 (STO), strontium ruthenate SrRuO 3 (SRO), and the like. These ceramic layers 10 have power generation characteristics due to shape changes (piezoelectric effect) and resistance changes due to shape changes (piezoresistive effect). The thickness of the ceramic layer 10 is preferably 20 nm to 800 nm. If it is too thick, the wrinkle structure 18 cannot be maintained.
本発明に係るフレキシブルセラミックス素子１は、セラミックス層１０の表面に皺構造１８を有する（図３（ｂ）も参照）。皺構造１８は、ピッチが１０μｍ～１００μｍ程度であり、皺の高さは概ね１μｍ～５０μｍ程度である。皺構造１８は、後述する製造基板２０の格子定数とセラミックス層１０の格子定数の差によって、セラミックス層１０に蓄積された応力が、製造基板２０を除去し解放されることで生じると考えられる。 The flexible ceramic element 1 according to the present invention has a wrinkle structure 18 on the surface of the ceramic layer 10 (see also FIG. 3(b)). The wrinkle structure 18 has a pitch of about 10 μm to 100 μm, and a wrinkle height of about 1 μm to 50 μm. It is thought that the wrinkle structure 18 is generated when the stress accumulated in the ceramic layer 10 is released by removing the manufacturing substrate 20 due to the difference between the lattice constant of the manufacturing substrate 20 and the ceramic layer 10, which will be described later.
この皺構造１８を有するため、本発明に係るフレキシブルセラミックス素子１は、素子に撓みや伸縮を与えても、緩衝層１２を含めてセラミックス層１０の皺構造１８が伸び、素子全体の撓みや伸縮に対して割れや破損を起こすことがない。 Since the flexible ceramic element 1 according to the present invention has this wrinkle structure 18, even if the element is subjected to deflection or expansion/contraction, the wrinkle structure 18 of the ceramic layer 10 including the buffer layer 12 will stretch, and the entire element will not be deflected or expanded/contracted. No cracking or damage will occur.
次に、本発明に係るフレキシブルセラミックス素子１の製造方法について図２を参照して説明する。まず、製造基板２０を用意する。製造基板２０はセラミックス層１０を形成するために用いる基板である。セラミックス層１０の結晶成長が行われやすく、後で溶解可能な材質がよい。より詳細には、溶解液で溶解し、セラミックス層１０を堆積させる処理面に特定結晶面が揃っている結晶性材料が好適に利用できる。具体的には、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＬａＭｎＯ３、Ｓｒ３Ａｌ２Ｏ６等が好適に利用できる。 Next, a method for manufacturing the flexible ceramic element 1 according to the present invention will be described with reference to FIG. 2. First, a manufacturing board 20 is prepared. The manufacturing substrate 20 is a substrate used to form the ceramic layer 10. A material that facilitates crystal growth of the ceramic layer 10 and can be melted later is preferable. More specifically, a crystalline material that is dissolved in a solution and has specific crystal planes aligned on the processing surface on which the ceramic layer 10 is deposited can be suitably used. Specifically, MgO, CaO, SrO, BaO, LaMnO 3 , Sr 3 Al 2 O 6 , etc. can be suitably used.
なお、他の材料の表面に、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯやＬａＭｎＯ３、Ｓｒ３Ａｌ２Ｏ６等を成膜して用いてもよい。その際、他の材料は溶解しなくてもよい。ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯやＬａＭｎＯ３、Ｓｒ３Ａｌ２Ｏ６等が溶解すればよいからである。 Note that a film of MgO, CaO, SrO, BaO, LaMnO 3 , Sr 3 Al 2 O 6 , etc. may be formed on the surface of other materials. At this time, other materials do not need to be dissolved. This is because MgO, CaO, SrO, BaO, LaMnO 3 , Sr 3 Al 2 O 6 , etc. need only be dissolved.
製造基板２０の処理面にセラミックス層１０を堆積させる（図２（ａ））。積層方法は特に限定されるものではないが、物理的気相法や化学的気相法が好適に利用できる。製造基板２０上に結晶構造を成長させやすいからである。例えば、プラズマＣＶＤ、パルスレーザー堆積（ＰＬＤ）、レーザーＭＢＥ、スパッタリング等が好適に利用できる。 A ceramic layer 10 is deposited on the processing surface of the manufacturing substrate 20 (FIG. 2(a)). Although the lamination method is not particularly limited, a physical vapor phase method or a chemical vapor phase method can be suitably used. This is because it is easier to grow a crystal structure on the manufacturing substrate 20. For example, plasma CVD, pulsed laser deposition (PLD), laser MBE, sputtering, etc. can be suitably used.
次にセラミックス層１０の上面に緩衝層１２を形成する（図２（ｂ））。緩衝層１２は、物理的気相法を利用することができ、スパッタリングや蒸着といった方法を好適に利用できる。 Next, a buffer layer 12 is formed on the upper surface of the ceramic layer 10 (FIG. 2(b)). For the buffer layer 12, a physical vapor phase method can be used, and methods such as sputtering and vapor deposition can be suitably used.
緩衝層１２の上面には、接着層１４を形成する（図２（ｃ））。接着層１４は、塗布や予め層状に形成された接着テープの接着が好適に利用できる。接着層１４の上面にフレキシブル基板１６を配置する（図２（ｄ））。従って、フレキシブル基板１６と、緩衝層１２およびセラミックス層１０を接着層１４がつなぎ合わせる構造となる。図２（ｄ）の状態を「積層物」と呼ぶ。 An adhesive layer 14 is formed on the upper surface of the buffer layer 12 (FIG. 2(c)). For the adhesive layer 14, coating or adhesion using an adhesive tape formed in a layered form in advance can be suitably used. A flexible substrate 16 is placed on the upper surface of the adhesive layer 14 (FIG. 2(d)). Therefore, the structure is such that the adhesive layer 14 connects the flexible substrate 16, the buffer layer 12, and the ceramic layer 10. The state shown in FIG. 2(d) is called a "laminate".
次にこの積層物を、溶解液３２を満たした処理槽３０中に浸漬させ、製造基板２０だけを選択的に溶解し除去する（図２（ｅ））。溶解液３２は、使用する製造基板２０によって変えてよい。この際に、セラミックス層１０、緩衝層１２、接着層１４、フレキシブル基板１６にダメージを与えないような溶解液３２を選択する必要がある。製造基板２０を除去すると、本発明に係るフレキシブルセラミックス素子１を得ることができる（図２（ｆ）、図２（ｇ））。 Next, this laminate is immersed in a processing tank 30 filled with a dissolving solution 32, and only the manufacturing substrate 20 is selectively dissolved and removed (FIG. 2(e)). The solution 32 may be changed depending on the manufacturing substrate 20 used. At this time, it is necessary to select a solution 32 that will not damage the ceramic layer 10, buffer layer 12, adhesive layer 14, and flexible substrate 16. When the manufacturing substrate 20 is removed, the flexible ceramic element 1 according to the present invention can be obtained (FIGS. 2(f) and 2(g)).
以下に本発明に係るフレキシブルセラミックス素子１の実施例を示す。製造基板２０にはＭｇＯ基板を用いた。ＭｇＯ基板は大きさが１０ｍｍ×１０ｍｍで厚さが０．５ｍｍのもので、処理面が（１００）面に形成されているものを用いた。 Examples of the flexible ceramic element 1 according to the present invention are shown below. An MgO substrate was used as the manufacturing substrate 20. The MgO substrate used had a size of 10 mm x 10 mm and a thickness of 0.5 mm, and the processed surface was formed as a (100) plane.
このＭｇＯ基板にパルスレーザー堆積（ＰＬＤ）法を用いてＢａＴｉＯ３セラミックス層を堆積させた。ＢａＴｉＯ３セラミックス層が、セラミックス層１０に相当する。使用したレーザーはＫｒＦエキシマレーザー（波長２４８ｎｍ）を用いた。薄膜原料のターゲットの化学組成は、ＢａＴｉＯ３である。この組成が全てＭｇＯ基板の処理面に成膜されるとした。 A BaTiO 3 ceramic layer was deposited on this MgO substrate using a pulsed laser deposition (PLD) method. The BaTiO 3 ceramic layer corresponds to the ceramic layer 10. The laser used was a KrF excimer laser (wavelength: 248 nm). The chemical composition of the thin film raw material target is BaTiO3 . It was assumed that all of this composition was formed into a film on the treated surface of the MgO substrate.
成膜直前のバックグラウンド圧力（到達真空度）は１０－５Ｐａで、成膜時には、純Ｏ２を分圧が１０－２Ｐａになるように導入した。成膜時の基板温度は８００℃、成膜レートは、膜厚が６０ｎｍまでは０．５ｎｍ／ｍｉｎ、膜厚が６０ｎｍから２４０ｎｍまでは１．５ｎｍ／ｍｉｎ、膜厚が２４０ｎｍから６００ｎｍまでは２．５ｎｍ／ｍｉｎとし、最終膜厚は６００ｎｍとした。 The background pressure (achieved vacuum degree) immediately before film formation was 10 −5 Pa, and pure O 2 was introduced at a partial pressure of 10 −2 Pa during film formation. The substrate temperature during film formation was 800°C, and the film formation rate was 0.5 nm/min for film thicknesses up to 60 nm, 1.5 nm/min for film thicknesses from 60 nm to 240 nm, and 2 nm/min for film thicknesses from 240 nm to 600 nm. .5 nm/min, and the final film thickness was 600 nm.
次に、緩衝層１２としてのＰｔ層を、ＢａＴｉＯ３セラミックス層の上面に形成した。Ｐｔ層は以下の条件の下、ＤＣスパッタリング法で形成した。基板温度は室温とし、成膜時の圧力は１０－１Ｐａ、成膜速度は１ｎｍ／ｍｉｎとし、最終膜厚は３０ｎｍとした。つまり、Ｐｔ層の形成には３０分のスパッタリングによって形成した。 Next, a Pt layer as a buffer layer 12 was formed on the top surface of the BaTiO 3 ceramic layer. The Pt layer was formed by DC sputtering under the following conditions. The substrate temperature was room temperature, the pressure during film formation was 10 −1 Pa, the film formation rate was 1 nm/min, and the final film thickness was 30 nm. That is, the Pt layer was formed by sputtering for 30 minutes.
次に接着層１４として、アクリル系粘着剤で構成された両面テープ（厚さ１００μｍ）をＰｔ層上面に貼り付けた。その後、接着層１４の上面に厚さ１００μｍのＰＥＴシートを貼り付けた。ＰＥＴシートはフレキシブル基板１６に相当する。 Next, as the adhesive layer 14, a double-sided tape (thickness: 100 μm) made of an acrylic adhesive was attached to the upper surface of the Pt layer. Thereafter, a 100 μm thick PET sheet was attached to the upper surface of the adhesive layer 14. The PET sheet corresponds to the flexible substrate 16.
次にこの積層体を４０℃に維持した濃度１０体積％のリン酸水溶液に浸漬させ、ＭｇＯ基板を溶解した。リン酸水溶液は溶解液３２に相当する。ＭｇＯ基板が溶解するのに、約２５時間から３０時間ほどかかった。このようにして得た本発明に係るフレキシブルセラミックス素子１の外観を図３（ｄ）に示し、その表面の顕微鏡写真を図３（ｂ）に示す。なお、図３（ｃ）および図３（ａ）は、緩衝層１２がない場合の写真である。 Next, this laminate was immersed in a 10% by volume phosphoric acid aqueous solution maintained at 40° C. to dissolve the MgO substrate. The phosphoric acid aqueous solution corresponds to the dissolving solution 32. It took about 25 to 30 hours for the MgO substrate to dissolve. The external appearance of the flexible ceramic element 1 according to the present invention thus obtained is shown in FIG. 3(d), and a microscopic photograph of its surface is shown in FIG. 3(b). Note that FIGS. 3(c) and 3(a) are photographs in the case where the buffer layer 12 is not provided.
図３（ｂ）を参照して、緩衝層１２を有する本発明に係るフレキシブルセラミックス素子１の表面には、皺構造１８が形成されている。一方、緩衝層１２を有していない場合は、図３（ａ）に示すようにセラミックス層１０の表面に割れ１９が発生していた。緩衝層１２を有することで、皺構造１８が形成され、その結果、セラミックス層１０に割れ１９が生じていない。 Referring to FIG. 3(b), a wrinkle structure 18 is formed on the surface of the flexible ceramic element 1 according to the present invention having a buffer layer 12. On the other hand, when the buffer layer 12 was not provided, cracks 19 were generated on the surface of the ceramic layer 10, as shown in FIG. 3(a). By having the buffer layer 12, a wrinkle structure 18 is formed, and as a result, no cracks 19 occur in the ceramic layer 10.
図４には、緩衝層１２がない場合の積層体（図４（ａ））および製造基板２０を除去した後（図４（ｂ））のＸ線回折の結果を表す。また、図５には緩衝層１２がある場合の積層体（図５（ａ））および製造基板２０を除去した後（図５（ｂ）：これがフレキシブルセラミックス素子１である。）のＸ線回折の結果を示す。図４、図５共に、横軸は２θ（ｄｅｇ．）であり、縦軸は強度（任意単位）である。 FIG. 4 shows the results of X-ray diffraction of the laminate without the buffer layer 12 (FIG. 4(a)) and after removing the manufacturing substrate 20 (FIG. 4(b)). In addition, FIG. 5 shows the X-ray diffraction of the laminate with the buffer layer 12 (FIG. 5(a)) and after removing the manufacturing substrate 20 (FIG. 5(b): this is the flexible ceramic element 1). The results are shown below. In both FIGS. 4 and 5, the horizontal axis is 2θ (deg.), and the vertical axis is intensity (arbitrary unit).
図４および図５を参照すると、製造基板２０を除去すると、製造基板２０の特性反射（２θで４１度、９５度付近）が消失するとともに、プラスチック（ＰＥＴフィルム）の特性反射が観測された。 Referring to FIGS. 4 and 5, when the manufacturing substrate 20 was removed, the characteristic reflection of the manufacturing substrate 20 (around 41 degrees and 95 degrees in 2θ) disappeared, and the characteristic reflection of the plastic (PET film) was observed.
また、セラミックス層１０の特性反射は、緩衝層１２のない図４では、（００１）面、（００２）面、（００３）面、（００４）面ともに低くなった。一方緩衝層１２のある図５においては、各面とも反射は低くなったものの、図４ほどではなく、明確にピークを確認することができた。 Further, in FIG. 4 without the buffer layer 12, the characteristic reflection of the ceramic layer 10 was low for all of the (001) plane, (002) plane, (003) plane, and (004) plane. On the other hand, in FIG. 5 with the buffer layer 12, although the reflection was lower on each surface, it was not as high as in FIG. 4, and a peak could be clearly observed.
図６には、セラミックス層１０の表面のレーザー顕微鏡像を示す。図３よりも倍率は高い。スケールバーは５０μｍである。皺構造１８は縦方向および横方向ともにおよそピッチ約５０μｍであった。 FIG. 6 shows a laser microscope image of the surface of the ceramic layer 10. The magnification is higher than in Figure 3. Scale bar is 50 μm. The wrinkle structure 18 had a pitch of approximately 50 μm in both the vertical and horizontal directions.
また、図７にはレーザー顕微鏡の鳥観図を示す。縦方向および横方向とも単位はμｍである。この鳥観図のＡの部分の断面図を図８に示す。図８を参照して横軸は長さ（μｍ）であり、縦軸は高さ（μｍ）である。このうち矢印の部分が皺構造になっている。このように、レーザー顕微鏡での観察で複数個所の皺構造１８の高さを測定するとおよそ５μｍ～１０μｍであった。 Moreover, FIG. 7 shows a bird's-eye view of the laser microscope. The unit is μm in both the vertical and horizontal directions. A cross-sectional view of part A of this bird's-eye view is shown in FIG. Referring to FIG. 8, the horizontal axis is length (μm), and the vertical axis is height (μm). The part indicated by the arrow has a wrinkled structure. As described above, when the heights of the wrinkle structures 18 at multiple locations were measured by observation using a laser microscope, the heights were approximately 5 μm to 10 μm.
ピッチ５０μｍで高さが５μｍの場合、この皺が平らになるまで伸ばすと２％伸び、高さが１０μｍであれば、７．６％程伸びることとなる。つまり、この程度の皺構造１８を有するセラミックス層１０であれば、見かけ上２～７．６％ほど伸びることとなる。このように本発明に係るフレキシブルセラミックス素子は、セラミックス素子でありながら、見かけ上伸縮させることができる。 If the pitch is 50 μm and the height is 5 μm, if the wrinkles are stretched out until they become flat, it will elongate by 2%, and if the height is 10 μm, it will elongate by about 7.6%. In other words, the ceramic layer 10 having the wrinkle structure 18 of this degree will apparently elongate by about 2 to 7.6%. As described above, the flexible ceramic element according to the present invention can apparently expand and contract, although it is a ceramic element.
本発明に係るフレキシブルセラミックス素子は、粘着性のある接着層を介してフレキシブル基板に転写された後にも結晶構造を維持することができ、さらに、皺構造を有するので、素子全体に撓みや伸縮が与えられても、セラミックス層に割れが入ることを抑制することができる。 The flexible ceramic element according to the present invention can maintain its crystal structure even after being transferred to a flexible substrate via a sticky adhesive layer, and furthermore, since it has a wrinkled structure, the entire element does not bend or expand/contract. Even if it is applied, cracks in the ceramic layer can be suppressed.
１ フレキシブルセラミックス素子
１０ セラミックス層
１２ 緩衝層
１４ 接着層
１６ フレキシブル基板
１８ 皺構造
２０ 製造基板
1 Flexible ceramic element 10 Ceramic layer 12 Buffer layer 14 Adhesive layer 16 Flexible substrate 18 Wrinkled structure 20 Manufacturing substrate
Claims (4)
前記フレキシブル基板上面に形成された接着層と、
前記接着層上面に形成された緩衝層と、
前記緩衝層上面に形成されたセラミックス層を有し、
前記セラミックス層には、ピッチが１０μｍ～１００μｍで高さが１μｍ～５０μｍの前記セラミックス層の皺から成る皺構造を有するフレキシブルセラミックス素子。 a flexible substrate,
an adhesive layer formed on the top surface of the flexible substrate;
a buffer layer formed on the top surface of the adhesive layer;
a ceramic layer formed on the upper surface of the buffer layer ;
A flexible ceramic element in which the ceramic layer has a wrinkle structure consisting of wrinkles of the ceramic layer with a pitch of 10 μm to 100 μm and a height of 1 μm to 50 μm.
前記セラミックス層の上面に緩衝層を形成する工程と、
前記緩衝層の上面に接着層を形成する工程と、
前記接着層の上面にフレキシブル基板を配置する工程と、
前記製造基板を除去し、ピッチが１０μｍ～１００μｍで高さが１μｍ～５０μｍの前記セラミックス層の皺から成る皺構造を付与する工程を有することを特徴とするフレキシブルセラミックス素子の製造方法。 a step of forming a ceramic layer on the treated surface of the manufacturing substrate;
forming a buffer layer on the top surface of the ceramic layer;
forming an adhesive layer on the top surface of the buffer layer;
arranging a flexible substrate on the top surface of the adhesive layer;
A method for manufacturing a flexible ceramic element, comprising the step of removing the manufacturing substrate and providing a wrinkled structure consisting of wrinkles of the ceramic layer having a pitch of 10 μm to 100 μm and a height of 1 μm to 50 μm.
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