JPS63279504A - Manufacture of ferroelectric thin film - Google Patents
Manufacture of ferroelectric thin filmInfo
- Publication number
- JPS63279504A JPS63279504A JP62114163A JP11416387A JPS63279504A JP S63279504 A JPS63279504 A JP S63279504A JP 62114163 A JP62114163 A JP 62114163A JP 11416387 A JP11416387 A JP 11416387A JP S63279504 A JPS63279504 A JP S63279504A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- tio2
- pbo
- monocrystal
- electric furnace
- 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 abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 23
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 229910000464 lead oxide Inorganic materials 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、圧電素子、電気光学素子、赤外線検出素子な
ど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 of manufacturing a ferroelectric thin film used for piezoelectric elements, electro-optical elements, infrared detection elements, etc.
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、圧電
素子、光変調素子、メモリ素子、赤外線検出素子などさ
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、強誘電体素子も小型化、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 piezoelectric elements, light modulation elements, memory elements, and infrared detection elements. As electronic components become smaller due to recent advances in semiconductor technology, ferroelectric elements are also becoming smaller and thinner.
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、Ｐｂ Ｔｉ ０３を形成させる方法が報
告されている（ Ｋ、Ｉｉｊｉｍａ（飯島賢二）他。To date, for example, magnesia (
A method for forming PbTiO3 on MgO) has been reported (K, Iijima et al.).
Ｊ、ムｐｐｌ 、 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〕。J, ppl, 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Ｐｂ Ｔｉ Ｏｓ薄膜は、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 Looking at the microstructure of a Pb Ti Os thin film formed by sputtering, the surface is extremely rough, the fractured surface has a columnar structure, and gaps are visible, and it cannot be said to be very dense (as described above). literature). Therefore, there is a limit to making the film thinner.
特に、光学的応用には不適である。一方、一般に化学気
相成長法（ｃｖｎ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、表面が平坦で高密度である
ことが期待される。In particular, it is unsuitable for optical applications. On the other hand, thin films formed by chemical vapor deposition (CVN) are generally formed under conditions close to thermal equilibrium conditions, and are therefore expected to have a flat surface and high density.
本発明は、気相からの析出と拡散を利用して、単結晶の
Ｔｉ ０２を基板に用い、その表面を、平坦で高密度の
Ｐｂ Ｔｉ ０５薄膜に変える方法に関するものである
。The present invention relates to a method of using single-crystal Ti 02 as a substrate and converting its surface into a flat, dense Pb Ti 05 thin film using precipitation and diffusion from the gas phase.
問題点を解決するだめの手段
ＴｉＯ２単結晶と酸化鉛ｐｂｏを入れたＭｇＯるつぼを
電気炉に入れ、昇温加熱することにより、Ｔｉ０２単結
晶の表面をＰｂＴｉ０．薄膜に変化させる。A solution to the problem: A MgO crucible containing a TiO2 single crystal and lead oxide pbo is placed in an electric furnace and heated to an elevated temperature, thereby changing the surface of the Ti02 single crystal to PbTi0. Change it into a thin film.
作用
本方法の気相からの析出と拡散により、１ｏ○〇への厚
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。Effect: Due to the deposition and diffusion from the gas phase of this method, a ferroelectric thin film having a sufficient dielectric strength voltage could be created even at a thickness of 1000 yen.
実施例
以下、本発明の一実施例について第１図を用いて説明す
る。EXAMPLE Hereinafter, an example of the present invention will be described with reference to FIG.
ＴｂＴｉＯ３薄膜を作成する材料兼基板として、Ｔｉ０
２（ルチル）単結晶板３を用いた。円柱形のＴｌＯ２単
結晶から円板の単結晶板を切りだした。Ti0 is used as a material and substrate for creating a TbTiO3 thin film.
2 (rutile) single crystal plate 3 was used. A circular single crystal plate was cut out from a cylindrical TlO2 single crystal.
Ｐｂ Ｔｉ Ｏ３を形成させる側を鏡面研磨し、スパッ
タエッチした。一方、ＰｂＯのガスを発生させる材料と
して、純度９９．９５％のｐｂｏ（リサージ）粉末４を
用いた。管状電気炉６中にアルミナ炉芯管６を入れ、炉
芯管６の中央付近に、Ｍｇ０（マグネシア）磁器ボート
１を置いた。ＭｇＯボート１にＰｂＯ粉末４を入れ、そ
の上にＭｇＯ磁器２板を置き、その上に上記Ｔｉｅ２結
晶板３を置いた。The side on which Pb Ti O 3 was to be formed was mirror polished and sputter etched. On the other hand, as a material for generating PbO gas, pbo (Lisurge) powder 4 with a purity of 99.95% was used. An alumina furnace core tube 6 was placed in a tubular electric furnace 6, and an Mg0 (magnesia) porcelain boat 1 was placed near the center of the furnace core tube 6. PbO powder 4 was placed in the MgO boat 1, two MgO porcelain plates were placed on top of it, and the Tie2 crystal plate 3 was placed on top of it.
電気炉の温度を上げ、ＰｂＯのガスを発生させＴｉ ０
２板と反応させた。電気炉の温度は、６００〜８５０’
Ｃの範囲で変化させた。反応時間は、０．５〜６時間で
ある。表面からＰｂ Ｔｉ ０５が成長する速度は、炉
の温度が高い程、また流す酸素ガス７の流量が大きい程
、大きい。８００’Ｃ以上で、酸素ガス流量が２００ｃ
ｃ／分（直径４．５Ｃｍの炉芯管）の場合、厚さ１００
μｍのＴｉＯ２の部分が、Ｐｂ Ｔｉ Ｏｓとなった。Raise the temperature of the electric furnace to generate PbO gas and Ti 0
It was reacted with two plates. The temperature of the electric furnace is 600-850'
It was varied within the range of C. The reaction time is 0.5 to 6 hours. The rate at which Pb Ti 05 grows from the surface increases as the temperature of the furnace increases and the flow rate of oxygen gas 7 increases. Above 800'C, oxygen gas flow rate is 200C
c/min (furnace core tube with diameter 4.5 cm), thickness 100
The μm TiO2 portion became Pb Ti Os.
Ｐｂ Ｔｉ ＯｓかどうかはＸ線解析で確かめた。 Ｐ
ｂＴｉＯ３とＴｉＯ２の厚みは、破断面をＸ線マイクロ
アナライザでしらべて見積った。It was confirmed by X-ray analysis whether it was Pb Ti Os. P
The thicknesses of bTiO3 and TiO2 were estimated by examining the fracture surface with an X-ray microanalyzer.
７ｏｏ℃で反応させて、ＰｂＴｉ０ｓ（７）厚みが、ｏ
、１゜１．１０．５０μｍの試料を作成した。The reaction was carried out at 70°C, and the thickness of PbTi0s(7) was
, 1°1.10.50 μm samples were prepared.
この方法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、平坦で柱状構造は見られなかった。表
面に２本の白金電極をスパッタ法で付け、分極して誘電
率ε、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。εｒとγを表１に示す。本方法で作成した
膜のＯ１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も高密度で、Ｏ
１もγも大きく・赤外検出素子などに用いたとき高性能
である。The surface of the thin film created using this method was observed using a scanning electron microscope. The surface was flat and no columnar structure was observed. Two platinum electrodes were attached to the surface by sputtering, polarized, and the dielectric constant ε and pyroelectric coefficient γ were measured and compared with the values of the film obtained by sputtering. Table 1 shows εr and γ. The O1 and γ of the film prepared by this method are clearly large. Therefore, the device fabricated by this method has a higher density than a film fabricated by sputtering, and
Both 1 and γ are large, resulting in high performance when used in infrared detection elements, etc.
表１ 本方法とスパッタ法の比較
法に、厚みを変えて、絶縁破壊電場Ｅ、をシリコン油中
で測定した。厚みが０．１μｍ以上では、ＥＢが１８０
ｋＶ／ｃｍ以上であった。スパッタ法で作成した薄膜
では、厚さが０．６μｍ以下になると急速に、ＥＢが低
下した。このように、本発明の方法では、かなり薄い平
坦な薄膜が作成できる。このことは、上記の赤外検出素
子や光学素子を作成する場合に、有利である。Table 1 Comparison between this method and sputtering method: The dielectric breakdown electric field E was measured in silicone oil with different thicknesses. When the thickness is 0.1 μm or more, EB is 180
It was more than kV/cm. In the thin film created by sputtering, the EB decreased rapidly when the thickness became 0.6 μm or less. Thus, the method of the present invention allows for the production of fairly thin and flat films. This is advantageous when producing the above-mentioned infrared detection element and optical 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、表面が平坦でさらに薄くできる。これは、高性能の
赤外検出素子、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 detection elements, piezoelectric elements, and electro-optic elements.
第１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・・・・・・Ｍｇ０（マグネシア）るつぼ、２・・・
・・・ＭｇＯ磁器、３・・・・・・Ｔｉ０２（ルチル）
単結晶基板、４・・川ｐｂｏ（−酸化鉛、リサージ）粉
末、６・・・・・・ｔ 気炉、６・・・・・・石英炉芯
管、７・・・・・・酸素ガス。FIG. 1 is a block diagram of a thin film forming method in an embodiment of the present invention. 1...Mg0 (magnesia) crucible, 2...
...MgO porcelain, 3...Ti02 (rutile)
Single crystal substrate, 4... Kawa pbo (-lead oxide, litharge) powder, 6...t air furnace, 6... quartz furnace core tube, 7... oxygen gas .
Claims (1)
に置き、加熱し、強誘電体（ＰｂＴｉＯ＿３）薄膜を基
板表面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。A method for producing a ferroelectric thin film, which comprises placing a TiO_2 single crystal substrate in lead oxide (PbO) powder and heating it to form a ferroelectric (PbTiO_3) thin film on the substrate surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114163A JPS63279504A (en) | 1987-05-11 | 1987-05-11 | Manufacture of ferroelectric thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114163A JPS63279504A (en) | 1987-05-11 | 1987-05-11 | Manufacture of ferroelectric thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63279504A true JPS63279504A (en) | 1988-11-16 |
Family
ID=14630740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62114163A Pending JPS63279504A (en) | 1987-05-11 | 1987-05-11 | Manufacture of ferroelectric thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63279504A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100813517B1 (en) | 2006-10-27 | 2008-03-17 | 삼성전자주식회사 | Method of manufacturing ferroelectric thin film for data storage and method of manufacturing ferroelectric recording media using the same method |
| KR100858093B1 (en) * | 2007-12-20 | 2008-09-10 | 삼성전자주식회사 | Method of manufacturing ferroelectric thin film for data storage and method of manufacturing ferroelectric recording media using the same method |
-
1987
- 1987-05-11 JP JP62114163A patent/JPS63279504A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100813517B1 (en) | 2006-10-27 | 2008-03-17 | 삼성전자주식회사 | Method of manufacturing ferroelectric thin film for data storage and method of manufacturing ferroelectric recording media using the same method |
| KR100858093B1 (en) * | 2007-12-20 | 2008-09-10 | 삼성전자주식회사 | Method of manufacturing ferroelectric thin film for data storage and method of manufacturing ferroelectric recording media using the same method |
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