JPS63145353A - Formation of ferroelectric mixed polymer - Google Patents
Formation of ferroelectric mixed polymerInfo
- Publication number
- JPS63145353A JPS63145353A JP29127186A JP29127186A JPS63145353A JP S63145353 A JPS63145353 A JP S63145353A JP 29127186 A JP29127186 A JP 29127186A JP 29127186 A JP29127186 A JP 29127186A JP S63145353 A JPS63145353 A JP S63145353A
- Authority
- JP
- Japan
- Prior art keywords
- ferroelectric
- polymer
- mixed
- mixed polymer
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims 2
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 3
- 229920001778 nylon Polymers 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 229920002721 polycyanoacrylate Polymers 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 14
- 230000010287 polarization Effects 0.000 abstract description 7
- 230000002269 spontaneous effect Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 3
- -1 polyvinylene fluoride Polymers 0.000 abstract description 2
- 239000004677 Nylon Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 3
- 230000005621 ferroelectricity Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 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
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は密着性の高い安定な特性の強誘電性薄膜の形成
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a ferroelectric thin film with high adhesion and stable characteristics.
本発明は強誘電性混合高分子薄膜の形成方法に関するも
のである。The present invention relates to a method for forming a ferroelectric mixed polymer thin film.
強誘電性物質の比誘電率は非常に大きく強誘電体はコン
デンサー材料として重要である。さらに圧電性、焦電性
などを有するので、メモリー、平面スピーカー、表示素
子への利用は広い。The dielectric constant of ferroelectric materials is very large, making them important as capacitor materials. Furthermore, since it has piezoelectricity and pyroelectricity, it can be widely used in memories, flat speakers, and display elements.
強誘電性高分子は、チタン酸バリウムなどの無機強誘電
体に比して容易に形成できる強誘電体である。Ferroelectric polymers are ferroelectric materials that can be formed more easily than inorganic ferroelectric materials such as barium titanate.
そのため、その利用範囲も広範囲なものとなる。Therefore, its range of use is wide-ranging.
強誘電性を示す高分子は、ＰＶＤＦ ：ポリフッ化ビニ
リデン、 Ｐ（ＶＤＦ＋ＴｒＦＥ ） ：フッ化ビニリ
デンとトリフッ化エチレンの共重合体Ｐ（ＶＤＦ＋Ｔｅ
ＦＥ ） ：フッ化ビニリデンとテトラフッ化エチレン
の共重合体、Ｐ（ＶＤＣＮ ＋ＶＡＣ） ：ビニリデ
ンシアナイドとビニリデンアセテートの共重合体等があ
る。Polymers exhibiting ferroelectricity include PVDF: polyvinylidene fluoride, P(VDF+TrFE): copolymer of vinylidene fluoride and trifluoroethylene, P(VDF+Te
FE): A copolymer of vinylidene fluoride and tetrafluoroethylene, P(VDCN +VAC): A copolymer of vinylidene cyanide and vinylidene acetate, etc.
その多くは、フッ素系の高分子であり、それらと基板、
または電極の密着性は低く、信頼性の高い安定な薄膜を
得ることは難しい。従って強誘電性高分子の優れた特性
を失わずにこの薄膜の改質をする必要がある。Most of them are fluorine-based polymers, and they and the substrate,
Alternatively, the adhesion of the electrode is low, making it difficult to obtain a reliable and stable thin film. Therefore, it is necessary to modify this thin film without losing the excellent properties of the ferroelectric polymer.
本発明では、かかる問題を解決する為下記のような手段
を用いた。In the present invention, the following means were used to solve this problem.
強誘電性混合高分子を作製するには強誘電性高分子と混
合性のよいもの、溶媒が共通であること、強誘電性をそ
こなわない為に比較的直線性の高い構造を有する非強誘
電性高分子を用いる必要がある。その目的の為にポリ塩
化ビニル等のポリビニル類、ナイロン類、ポリイミド類
、ポリアクリロニトリル、ポリエーテルアミドなどを非
強誘電性高分子として用いるのが有用である。To make a ferroelectric mixed polymer, it is necessary to use a material that has good miscibility with the ferroelectric polymer, a common solvent, and a non-ferroelectric material with a relatively highly linear structure so as not to impair ferroelectricity. It is necessary to use dielectric polymers. For this purpose, it is useful to use polyvinyls such as polyvinyl chloride, nylons, polyimides, polyacrylonitrile, polyetheramide, etc. as non-ferroelectric polymers.
これらとＰ（ＶＤＦ＋ＴｅＦＥ ）などの強誘電体を強
誘電体：非強誘電性高分子８〜８：２の割合の混合溶液
から加熱成膜することにより基板に対して密着性の高い
、安定した強誘電性混合高分子薄膜を得ることがｔきる
ことを特徴とする。この場合、混合比により自発分極の
大きさの制御をすることが可能である。By heating these and a ferroelectric material such as P(VDF+TeFE) from a mixed solution of ferroelectric material and non-ferroelectric polymer in a ratio of 8 to 8:2, a stable film with high adhesion to the substrate is formed. It is characterized in that it is possible to obtain a ferroelectric mixed polymer thin film. In this case, it is possible to control the magnitude of spontaneous polarization by adjusting the mixing ratio.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
２００ｇのＰ （ＶＤＦ−トＴｅＦＥ ）を１０１のＮ
−メチル−２−ピロリドン中に入れ加熱溶解させる。次
にこれを日立化成（株） ＰＩＱ ５１と混合し、８０
℃で十分混和させ、濾過したものを混合高分子溶液とす
る。200 g of P (VDF-TeFE) to 101 N
- Place in methyl-2-pyrrolidone and heat to dissolve. Next, this was mixed with Hitachi Chemical Co., Ltd. PIQ 51, and 80
Mix thoroughly at ℃ and filter to obtain a mixed polymer solution.
この場合高分子の重量比はＰ（ＶＤＦ＋ＴｅＦＥ）
： ＰＩＱ＝２：１となる。In this case, the weight ratio of the polymer is P(VDF+TeFE)
: PIQ=2:1.
これをパターニングした電極を有するガラス基板上にス
ピンコードし、２００℃で２時間加熱し、強誘電性混合
薄膜を作製した。This was spin-coded onto a glass substrate having patterned electrodes and heated at 200° C. for 2 hours to produce a ferroelectric mixed thin film.
この薄膜の厚さは２０００人であった。The thickness of this thin film was 2000.
さらに蒸着法またはスパッタ法によりＡＩ、またはＣｒ
を成膜した。その上にレジストを塗布しフォトリソグラ
フィによりパターニング、エツチングし、上部電極を形
成した。この工程においても混合薄膜は剥離することも
なく、本発明によりその密着性や、耐溶材性が著しく向
上した。Furthermore, AI or Cr is added by vapor deposition or sputtering.
was deposited. A resist was applied thereon and patterned and etched by photolithography to form an upper electrode. Even in this step, the mixed thin film did not peel off, and the present invention significantly improved its adhesion and resistance to solvents.
この試料の自発分極をＤ−Ｅヒステリシスループ法によ
り測定した。The spontaneous polarization of this sample was measured by the DE hysteresis loop method.
自発分極は３００ ｎＣ／ｃ４であった。混合比を２二
８〜８：２まで変化させることにより自発分極は８０〜
５０００Ｃ／ｃＩ１１と変化する。これは本来のＰ（Ｖ
ＤＦ＋ＴｅＦＥ ）の自発分極数μＣ／ｃｎｌと混合比
から計算される自発分極の値より１ケタ程度は下がって
いる。非強誘電性高分子を混合することにより、結晶化
度が低下している為である。Spontaneous polarization was 300 nC/c4. By changing the mixing ratio from 228 to 8:2, the spontaneous polarization can be increased from 80 to 8:2.
It changes to 5000C/cI11. This is the original P(V
It is about one order of magnitude lower than the spontaneous polarization value calculated from the spontaneous polarization number μC/cnl of DF+TeFE) and the mixing ratio. This is because the degree of crystallinity is reduced by mixing the non-ferroelectric polymer.
しかし本混合膜は基板との密着性や、耐溶材性が向上し
数千人の薄膜にもかかわらずピンホールの少ない安定し
た強誘電性高分子薄膜が得られた。However, this mixed film has improved adhesion to the substrate and resistance to solvents, and a stable ferroelectric polymer thin film with few pinholes was obtained despite the thin film made by several thousand people.
本発明は強誘電性高分子と非強誘電性高分子の混合した
ことを特徴とするものである。本発明により下地其仮に
対する薄膜の密着性が従来に比べて格段に向上し、さら
に有機溶媒に対する薄膜の信頬性も向上した。The present invention is characterized by a mixture of ferroelectric polymer and non-ferroelectric polymer. According to the present invention, the adhesion of the thin film to the base material is significantly improved compared to the conventional method, and the reliability of the thin film to organic solvents is also improved.
このためピンホールの少ない安定な強誘電性高分子薄膜
を大面積其板上に容易に形成することが可能となった。Therefore, it has become possible to easily form a stable ferroelectric polymer thin film with few pinholes on a large-area substrate.
Claims (1)
強誘電性高分子と非強誘電性高分子の混合高分子を形成
することを特徴とする強誘電性混合高分子の形成方法。 ２、特許請求の範囲第１項記載の形成方法において、前
記非強誘電性高分子がポリビニル類、ポリイミド類、ポ
リエーテルアミド、ナイロン類、ポリシアノアクリレイ
トのうちから選ばれた１種類またはそれらの混合物であ
ることを特徴とする強誘電性混合高分子の形成方法。 ３、特許請求の範囲第１項において前記強誘電性高分子
と非強誘電性高分子の混合比が、４：１から１：４の範
囲にある強誘電性混合高分子の形成方法。[Claims] 1. Formation of a ferroelectric mixed polymer characterized by forming a mixed polymer of a fluorine-based or other ferroelectric polymer such as polyvinylidene fluoride and a non-ferroelectric polymer. Method. 2. In the forming method according to claim 1, the nonferroelectric polymer is one selected from polyvinyls, polyimides, polyetheramides, nylons, and polycyanoacrylates, or one of them. A method for forming a ferroelectric mixed polymer characterized by being a mixture of. 3. A method for forming a ferroelectric mixed polymer according to claim 1, wherein the mixing ratio of the ferroelectric polymer and the non-ferroelectric polymer is in the range of 4:1 to 1:4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291271A JP2660279B2 (en) | 1986-12-06 | 1986-12-06 | Method of forming ferroelectric polymer thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61291271A JP2660279B2 (en) | 1986-12-06 | 1986-12-06 | Method of forming ferroelectric polymer thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63145353A true JPS63145353A (en) | 1988-06-17 |
| JP2660279B2 JP2660279B2 (en) | 1997-10-08 |
Family
ID=17766712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61291271A Expired - Lifetime JP2660279B2 (en) | 1986-12-06 | 1986-12-06 | Method of forming ferroelectric polymer thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2660279B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0947555A1 (en) * | 1998-04-01 | 1999-10-06 | AUSIMONT U.S.A., Inc. | Compatible polyvinylidene fluoride blends with polymers containing imide moieties |
| EP0947556A1 (en) * | 1998-04-01 | 1999-10-06 | AUSIMONT U.S.A., Inc. | Compatible blends of polyvinylidene fluoride and aromatic polyimide |
| CN1067796C (en) * | 1995-09-11 | 2001-06-27 | 四川联合大学 | Method for prepn. of odd number nylon iron electric body |
| JP2018505929A (en) * | 2014-12-17 | 2018-03-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Printable ferroelectric ink |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56152103A (en) * | 1980-04-24 | 1981-11-25 | Kureha Chemical Ind Co Ltd | Improved dielectric film |
| JPS5744646A (en) * | 1980-07-23 | 1982-03-13 | Minnesota Mining & Mfg | Pyroelectric and isotropic piezoelectric polymer blend |
| JPS57141462A (en) * | 1981-02-25 | 1982-09-01 | Nippon Oil & Fats Co Ltd | Paint composition for precoated metal |
| JPS57153057A (en) * | 1981-03-18 | 1982-09-21 | Nippon Oil & Fats Co Ltd | Paint composition for precoated metal |
| JPS57187344A (en) * | 1981-05-12 | 1982-11-18 | Kureha Chem Ind Co Ltd | Resin composition |
| JPS57202789A (en) * | 1981-06-08 | 1982-12-11 | Japan Synthetic Rubber Co Ltd | Composite piezoelectric material |
| JPS5966465A (en) * | 1982-09-16 | 1984-04-14 | ソルヴアイ・エ・コンパニ−・ソシエテ・アノニム | Clear lacquer based on polyvinylidene fluoride and method ofpainting metal surface |
| JPS6148983A (en) * | 1984-08-16 | 1986-03-10 | Toray Ind Inc | Ferrodielectric high polymer thin film |
| JPS6197308A (en) * | 1984-10-17 | 1986-05-15 | Daikin Ind Ltd | Polymeric material for pyroelectric engine |
-
1986
- 1986-12-06 JP JP61291271A patent/JP2660279B2/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56152103A (en) * | 1980-04-24 | 1981-11-25 | Kureha Chemical Ind Co Ltd | Improved dielectric film |
| JPS5744646A (en) * | 1980-07-23 | 1982-03-13 | Minnesota Mining & Mfg | Pyroelectric and isotropic piezoelectric polymer blend |
| JPS57141462A (en) * | 1981-02-25 | 1982-09-01 | Nippon Oil & Fats Co Ltd | Paint composition for precoated metal |
| JPS57153057A (en) * | 1981-03-18 | 1982-09-21 | Nippon Oil & Fats Co Ltd | Paint composition for precoated metal |
| JPS57187344A (en) * | 1981-05-12 | 1982-11-18 | Kureha Chem Ind Co Ltd | Resin composition |
| JPS57202789A (en) * | 1981-06-08 | 1982-12-11 | Japan Synthetic Rubber Co Ltd | Composite piezoelectric material |
| JPS5966465A (en) * | 1982-09-16 | 1984-04-14 | ソルヴアイ・エ・コンパニ−・ソシエテ・アノニム | Clear lacquer based on polyvinylidene fluoride and method ofpainting metal surface |
| JPS6148983A (en) * | 1984-08-16 | 1986-03-10 | Toray Ind Inc | Ferrodielectric high polymer thin film |
| JPS6197308A (en) * | 1984-10-17 | 1986-05-15 | Daikin Ind Ltd | Polymeric material for pyroelectric engine |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067796C (en) * | 1995-09-11 | 2001-06-27 | 四川联合大学 | Method for prepn. of odd number nylon iron electric body |
| EP0947555A1 (en) * | 1998-04-01 | 1999-10-06 | AUSIMONT U.S.A., Inc. | Compatible polyvinylidene fluoride blends with polymers containing imide moieties |
| EP0947556A1 (en) * | 1998-04-01 | 1999-10-06 | AUSIMONT U.S.A., Inc. | Compatible blends of polyvinylidene fluoride and aromatic polyimide |
| US6313222B1 (en) | 1998-04-01 | 2001-11-06 | Ausimont Usa, Inc. | Compatible blends of polyvinylidene fluoride and aromatic polyimide |
| JP2018505929A (en) * | 2014-12-17 | 2018-03-01 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Printable ferroelectric ink |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2660279B2 (en) | 1997-10-08 |
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