JPS63178408A - Manufacture of ferro dielectric thin film - Google Patents
Manufacture of ferro dielectric thin filmInfo
- Publication number
- JPS63178408A JPS63178408A JP62010572A JP1057287A JPS63178408A JP S63178408 A JPS63178408 A JP S63178408A JP 62010572 A JP62010572 A JP 62010572A JP 1057287 A JP1057287 A JP 1057287A JP S63178408 A JPS63178408 A JP S63178408A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- manufacture
- dielectric thin
- elements
- sputtering
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000758 substrate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は焦電形赤外線検出素子、圧電素子、電気光学素
子に用いられる強誘電体薄膜の製造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 manufacturing a ferroelectric thin film used in pyroelectric infrared detection elements, piezoelectric elements, and electro-optical elements.
従来の技術
強誘電体のエレクトロニクス分野における応用は、赤外
線検出素子、圧電素子、光変調素子、メモリ素子などさ
まざまなものがある。近年の半導体技術の進歩による電
子部品の小型化にともない、強誘電体素子も薄膜化が進
みつつある。BACKGROUND ART There are various applications of ferroelectric materials in the electronics field, such as infrared detection elements, piezoelectric elements, light modulation elements, and memory elements. As electronic components become smaller due to advances in semiconductor technology in recent years, ferroelectric elements are also becoming thinner.
ところで、強誘電体の自発分極ｐｓ の変化を出力とし
て取りだす、例えば焦電形赤外線検出素子や圧電素子等
では、強誘電体材料のＰｓが一方向に揃っている（配向
している）とき、最も大きい出力が得られる。また出力
は薄膜が高密度であるほど太きい。By the way, in, for example, a pyroelectric infrared detection element or a piezoelectric element that outputs changes in the spontaneous polarization ps of a ferroelectric material, when the Ps of the ferroelectric material is aligned (orientated) in one direction, Maximum output can be obtained. Also, the higher the density of the thin film, the greater the output.
現在までに、例えば、スパッタリング法でマグネシア（
ＭｇＯ）上に、ＰｂＴｉ０３を形成させる方法が報告さ
れている（ ［、Ｉｉｊｉｍａ （飯島賢二）他、Ｊ、
ムｐＩ）ｌ 、Ｐｈｙｓ 、（ジャーナル・オブ・アプ
ライド・フィジックス） Ｖｏｌ 、 ６０．ｐ 、３
６１．１９８６年〕。To date, for example, magnesia (
A method for forming PbTi03 on MgO) has been reported ([, Iijima (Kenji Iijima) et al., J.
Phys, (Journal of Applied Physics) Vol. 60. p, 3
61.1986].
発明が解決しようとする問題点
スパッタで形成したＰｂＴｉｏ３薄膜は、Ｃ軸に配向し
ている（例えば、配向率９８％）が、その微細構造をみ
ると表面は、極めて粗く、破断面も柱状構造ですきまが
見え、あまり高密度とはいえない（前記文献）。従って
薄膜化にも限界がある。Problems to be Solved by the Invention The PbTio3 thin film formed by sputtering is oriented along the C axis (for example, the orientation rate is 98%), but when looking at its microstructure, the surface is extremely rough, and the fractured surface also has a columnar structure. Since gaps are visible, it cannot be said that the density is very high (see the above-mentioned document). Therefore, there is a limit to how thin the film can be made.
一方、一般に化学気相成長法（ＣＶＤ法）で作成した薄
膜は、熱平衡条件に近い条件で作成されるため、表面が
平担で高密度であることが期待される。従って、スパッ
タリング法よりも薄い薄膜が作成できる。On the other hand, thin films formed by chemical vapor deposition (CVD) are generally formed under conditions close to thermal equilibrium conditions, and are therefore expected to have a flat surface and high density. Therefore, thinner films can be created than with the sputtering method.
本発明は、化学気相成長によりその特長である平担性と
高密度性をそなえた高性能のｐｂｒｉｏ ５薄膜を作成
する方法を提供することを目的とするものである。An object of the present invention is to provide a method for producing a high-performance pbrio 5 thin film with its characteristics of flatness and high density by chemical vapor deposition.
問題点を解決するための手段
この目的を達成するために本発明は原料に、酸化鉛（Ｐ
ｂＯ）と有機金属Ｔｉ （チタニウム・テトラ−ｎ−プ
トキシド： Ｔｉ（Ｃ４Ｈ，０）４）を用イ、基板にマ
グネシア単結晶（ＭｇＯ）上にスパッタリングにより、
白金を成膜したものを用い、ｃｖｎ法でＰｂＴｉ０３薄
膜を成長させるものである。Means for Solving the Problems In order to achieve this object, the present invention uses lead oxide (P) as a raw material.
bO) and organometallic Ti (titanium tetra-n-poxide: Ti(C4H,0)4) were sputtered onto a magnesia single crystal (MgO) substrate.
A PbTi03 thin film is grown by the CVN method using a platinum film.
作用
ＣＶＤ法で成膜させることにより、１０００ムの厚みで
も、十分な絶縁耐圧を有する強誘電体薄膜が作成できた
。By forming the film using the active CVD method, a ferroelectric thin film having a sufficient dielectric strength even with a thickness of 1000 μm was created.
実施例
（１ｏｏ ）でへき関し鏡面研摩したＭｇＯ単結晶を基
板とし、下部電極として膜厚０．２μｍのｐｔ薄膜をス
パッタリングにより形成した。Using the MgO single crystal which had been mirror-polished in Example (1oo) as a substrate, a PT thin film having a thickness of 0.2 μm was formed as a lower electrode by sputtering.
ＭｇＯのボート形るつぼに、酸化鉛（ＰｂＯ）の粉末を
入れ、その上に、ＭｇＯのブロックを置き、このブロッ
ク上に基板を並べた。ＰｂＯを入れたボート形るつぼを
アルミナ炉心管の中央におき、その上にアルミナパイプ
を配置した。チタニウム・テトラ・ｎ・ブトキシド液体
をバブラーに入れ、２２０℃に加熱した。キャリアガス
としてムｒを用い、このＴ１の有機金属ガスをアルミナ
パイプを通して、反応炉に入れた。一方、Ｈ２Ｏはバブ
ラーに入れ、０２ガスをキャリアガスにして、反応炉に
入れた。ＣＶＤ法の条件を表１に示す。Lead oxide (PbO) powder was placed in an MgO boat-shaped crucible, an MgO block was placed on top of the powder, and the substrates were arranged on top of this block. A boat-shaped crucible containing PbO was placed in the center of an alumina furnace tube, and an alumina pipe was placed above it. Titanium tetra n-butoxide liquid was placed in a bubbler and heated to 220°C. Using Mr as a carrier gas, this T1 organometallic gas was introduced into the reactor through an alumina pipe. On the other hand, H2O was put into a bubbler, 02 gas was used as a carrier gas, and the mixture was put into the reactor. Table 1 shows the conditions of the CVD method.
（以 下金 白）
表１ ＣＶＤ法によるＰｂＴｉ０３薄膜の作成条件表２
に、基板温度、即ちｐｂｏを入れたるつぼの温度を変え
たときの、Ｘ線解析の結果を示す。(Hereinafter referred to as Gold White) Table 1 Table 2 Conditions for creating PbTi03 thin film by CVD method
2 shows the results of X-ray analysis when the substrate temperature, that is, the temperature of the crucible containing pbo, is changed.
（以下金 白）
基板温度が４００〜５００ ’Ｃではアモルファス、７
００ ’Ｃ以上では酸化鉛相が現れる。従って、ＰｂＴ
ｉＯ３の作成温度は５５Ｃ）〜６５０℃であるといえる
。(Hereinafter referred to as gold white) When the substrate temperature is 400 to 500'C, it becomes amorphous, 7
Above 00'C, a lead oxide phase appears. Therefore, PbT
It can be said that the production temperature of iO3 is 55C) to 650C.
ＣＶＩ）で作成した薄膜の表面を走査形電子顕微鏡で観
察した。表面は、平担で柱状構造はみられなかった。表
面に白金電極を付け、誘電率ε１と焦電係数γを測定し
、スパッタ法で得た膜の値と比較した。ε、とγを表３
に示す。本方法で作成した膜のεｒとγは明らかに大き
い。従って本方法で作成した素子は、スパッタ法で作成
した膜より高密度で、Ｃ１もγも大きく、焦電形赤外線
検出素子などに用いたとき高性能である。The surface of the thin film prepared using CVI) was observed using a scanning electron microscope. The surface was flat and no columnar structure was observed. A platinum electrode was attached to the surface, and the dielectric constant ε1 and pyroelectric coefficient γ were measured and compared with the values of a film obtained by sputtering. Table 3 shows ε and γ.
Shown below. The εr and γ of the film prepared by this method are clearly large. Therefore, the element produced by this method has a higher density than a film produced by sputtering, has larger C1 and γ, and has higher performance when used in a pyroelectric infrared detection element.
表３ ＣＶＤ法とスパッタ法の比較
次に、厚みを変えて、絶縁破壊電場ＥＢを測定した。厚
みが１０００Ａ以上では、Ｔ！、Ｂが２００ｋｖ／（７
）以上あった。スパッタ法により作成した薄膜では、厚
さが５０００Ａ以下になると急速にＥ、が低下した。こ
のように、ＣＶＤ法ではかなり薄い平担な薄膜が作成で
きる。このことは、上記の赤外検出素子を作成する場合
に、有利である。Table 3 Comparison of CVD method and sputtering method Next, the dielectric breakdown electric field EB was measured while changing the thickness. If the thickness is 1000A or more, T! , B is 200kv/(7
) There were more than that. In the thin film created by sputtering, E rapidly decreased when the thickness became 5000A or less. In this way, the CVD method can produce a fairly thin and flat thin film. This is advantageous when producing the above-mentioned infrared detection element.
発明の効果
本発明の強誘電体薄膜は高密度で、大きい焦電係数をも
ち、表面が平担でさらに薄くできる。これは高性能の赤
外線検出素子、圧電素子、電気光学素子をもたらす。Effects of the Invention The ferroelectric thin film of the present invention has a high density, a large pyroelectric coefficient, a flat surface, and can be made even thinner. This results in high performance infrared sensing elements, piezoelectric elements, and electro-optical elements.
図は本発明の実施例における薄膜作成法の構成図である
。
１・・・・・・マグネジするつぼ、２・・・・・・マグ
ネシア磁器、３・・・・・・基板、４・・・・・・ｐｂ
ｏ粉末、６・・・・・電気炉、６・・・・・・アルミナ
（’６２Ｃ’３）パイプ、７・・・・ガスｌ（Ｏ□＋Ｈ
２０）、８−・−−ガス１１（人ｒ＋Ｔ ｉ （Ｃ４Ｈ
，Ｏ） 、 ）。The figure is a block diagram of a thin film forming method in an embodiment of the present invention. 1...magnetic pot, 2...magnesia porcelain, 3...substrate, 4...pb
o powder, 6... electric furnace, 6... alumina ('62C'3) pipe, 7... gas l (O□+H
20), 8-・--Gas 11 (person r+T i (C4H
,O), ).
Claims (1)
有機金属（チタニウム−テトラ−ｎ−プトキシド、Ｔｉ
（Ｃ＿４Ｈ＿９Ｏ）＿４）ガス中で、加熱しＰｂＴｉＯ
＿３からなる強誘電体薄膜を基板上に形成させることを
特徴とする強誘電体薄膜の製造方法。The substrate is placed in lead oxide (PbO) powder, and a Ti organometallic (titanium-tetra-n-poxide, Ti
(C_4H_9O)_4) Heat PbTiO in gas
A method for producing a ferroelectric thin film, the method comprising forming a ferroelectric thin film comprising _3 on a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62010572A JPS63178408A (en) | 1987-01-20 | 1987-01-20 | Manufacture of ferro dielectric thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62010572A JPS63178408A (en) | 1987-01-20 | 1987-01-20 | Manufacture of ferro dielectric thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63178408A true JPS63178408A (en) | 1988-07-22 |
Family
ID=11753949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62010572A Pending JPS63178408A (en) | 1987-01-20 | 1987-01-20 | Manufacture of ferro dielectric thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63178408A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686151A (en) * | 1993-09-14 | 1997-11-11 | Kabushiki Kaisha Toshiba | Method of forming a metal oxide film |
| US5993901A (en) * | 1993-01-20 | 1999-11-30 | Murata Manufacturing Co., Ltd. | Production of thin films of a lead titanate system |
-
1987
- 1987-01-20 JP JP62010572A patent/JPS63178408A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5993901A (en) * | 1993-01-20 | 1999-11-30 | Murata Manufacturing Co., Ltd. | Production of thin films of a lead titanate system |
| US5686151A (en) * | 1993-09-14 | 1997-11-11 | Kabushiki Kaisha Toshiba | Method of forming a metal oxide film |
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