JPS61285609A - Lead titanate ferrodielectric thin film and manufacture thereof - Google Patents
Lead titanate ferrodielectric thin film and manufacture thereofInfo
- Publication number
- JPS61285609A JPS61285609A JP12845685A JP12845685A JPS61285609A JP S61285609 A JPS61285609 A JP S61285609A JP 12845685 A JP12845685 A JP 12845685A JP 12845685 A JP12845685 A JP 12845685A JP S61285609 A JPS61285609 A JP S61285609A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- lead titanate
- present
- manufacture
- dielectric
- 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
- 239000010409 thin film Substances 0.000 title claims description 47
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 description 17
- 238000010304 firing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical group 0.000 description 7
- 229910003781 PbTiO3 Inorganic materials 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- -1 Furthermore Chemical compound 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemically Coating (AREA)
- 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、チタン酸鉛（ＰｂＴｉＯｓ）強誘電体薄ｎり
に係り、さらに詳しくは、組成として、Ｍ ｎ Ｏｔ
＋ Ｌ ａ ｚ Ｏ３お。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to lead titanate (PbTiOs) ferroelectric thin film, and more specifically, the composition is M n Ot
+ L az O3.
よび５ｉ０２よりなる群から選ばれた少なくとも１種の
金属酸化物を含有するチタン酸鉛強誘電体薄膜およびそ
の塗布焼成法による製造方法に関する。The present invention relates to a lead titanate ferroelectric thin film containing at least one metal oxide selected from the group consisting of
本発明のチタン酸鉛強誘電体薄膜は、薄膜コンデンサー
、薄膜焦電素子等として有用である。The lead titanate ferroelectric thin film of the present invention is useful as a thin film capacitor, a thin film pyroelectric element, and the like.
従来、強誘電体を用いた熱形の焦電素子として、セラミ
ックス粉焼結体や単結晶を用いたものが既に実用化され
ている。Conventionally, as a thermal type pyroelectric element using a ferroelectric substance, one using a ceramic powder sintered body or a single crystal has already been put into practical use.
一方、実用的な絶縁耐圧の得られる薄膜コンデンサー用
の誘電体として、Ｔａｇ’ｓ 、Ｓ＋３Ｎａ等がＩＣ等
に使用されている。On the other hand, Tag's, S+3Na, and the like are used in ICs and the like as dielectric materials for thin film capacitors that have a practical dielectric strength.
焦電素子を目的として、スパッタリング法により製造し
た、［、ａｔＯｓまたはＭｎ０ｔを添加したＰｂＴｉＯ
ｓ薄膜が、特開昭５９−１４１２７号公報および特開昭
５９−１３８００４号公報に記載されている。PbTiO doped with [, atOs or Mn0t, manufactured by sputtering method for the purpose of pyroelectric elements.
s thin films are described in JP-A-59-14127 and JP-A-59-138004.
また、本出願人は、船倉を複合オキジアルコキシドの均
一な溶液を使用する、塗布焼成法によるＰｂＴ ｉｏｗ
ｌ膜の製造方法を、先に提案した。（特開昭５８−１３
８６９号公報参照）
〔発明が解決しようとする問題点〕
焦電素子は、薄いほど熱容量が下がり感度が増加するた
め、薄膜焦電素子が要望されている。In addition, the present applicant has prepared PbT iow in a ship hold by a coating and firing method using a homogeneous solution of composite oxydialkoxide.
A method for manufacturing the l membrane was previously proposed. (Unexamined Japanese Patent Publication No. 58-13
(See Publication No. 869) [Problems to be Solved by the Invention] Since the thinner the pyroelectric element is, the lower the heat capacity and the higher the sensitivity, a thin film pyroelectric element is desired.
従来、焦電素子に使用されている単結晶やセラミックス
粉焼結体では、加工性に問題があってあまり薄くするこ
とはできない。Single crystals and ceramic powder sintered bodies conventionally used in pyroelectric elements have problems with workability and cannot be made very thin.
一方、薄膜コンデンサーとして、ＩＣ等に使用されてい
るＴａＪｚ、５ｉＪａ等は、比誘電率：εが約２０以下
と小さく実用的でない。On the other hand, thin film capacitors such as TaJz and 5iJa used in ICs and the like have a relative dielectric constant: ε of about 20 or less, which is not practical.
また、積層コンデンサーに使用されている高εの多成分
系セラミックス粉焼結体では、前記焦電素子の場合と同
様に加工性に問題があり、薄膜を形成することが極めて
困難である。 ＢａＴｉ０ｔ、５ｒＴｉＯｔ系では、焼
結温度が高く、セラミックスと同等のＣを持つ薄膜を作
ることは困難である。Further, the high ε multi-component ceramic powder sintered body used in multilayer capacitors has problems in processability, as in the case of the pyroelectric element, and it is extremely difficult to form a thin film. In BaTiOt and 5rTiOt systems, the sintering temperature is high, and it is difficult to create a thin film with C equivalent to that of ceramics.
ＰｂＴｉ０ａは、キューリ一点が約５００℃と高く、ε
も強誘電体の中では約２００と比較的に小さく、焦電材
料として優れている。 また、ＰｂＴｉ０：＋は成分が
単純であり、焼結温度もＢａＴｉＯｓ、５ｒＴｉＯ＝に
比べ低い。PbTi0a has a single curie point as high as approximately 500°C, and ε
Among ferroelectric materials, it is relatively small at about 200, making it an excellent pyroelectric material. Furthermore, PbTi0:+ has simple components and its sintering temperature is lower than that of BaTiOs and 5rTiO=.
したがって、ＰｂＴｉＯｓは、セラミックス粉焼結体と
同等のεを持ち、かつ、セラミックス以上の絶縁耐性を
持つ薄膜が得られれば、焦電素子としても、また、薄膜
コンデンサー用の誘電体としても極めて有用である。Therefore, PbTiOs would be extremely useful as a pyroelectric element and as a dielectric for thin film capacitors if a thin film with ε equivalent to that of ceramic powder sintered bodies and insulation resistance greater than that of ceramics could be obtained. It is.
特性の良いＰｂＴｉ０ｚ薄膜を得るために、ストイキオ
メトリ制御が重要であるが、スパッタリング法、真空蒸
着法によるＰｂＴｉＯ３薄膜の製造においては、その制
御が極めて困難である。In order to obtain a PbTiOz thin film with good properties, stoichiometry control is important, but it is extremely difficult to control when producing a PbTiO3 thin film by sputtering or vacuum evaporation.
また、前記引用した公報には、スパッタリング法におい
て特性を向上させるために、ＰｂＴｉ０＋薄膜に、Ｌａ
ｔ、ｓまたはＭｎＯ□のいずれかを添加物として加える
方法を提案しているが、比抵抗、絶縁耐圧および誘ｉｉ
ｔＭ失の全てについて満足できる値を持つ薄膜は得られ
ていない。In addition, in the above-cited publication, in order to improve the characteristics in the sputtering method, La
A method of adding either t, s or MnO□ as an additive is proposed, but specific resistance, dielectric strength voltage and
A thin film with satisfactory values for all tM losses has not been obtained.
一方、本出願人の提案した塗布焼成法は、溶液法であり
、かつ、低温焼成が可能であるため、ストイキオメトリ
制御が容易であり、セラミックス粉焼結体と同等の比抵
抗、絶縁耐性等の特性を持つＰｂＴｉ０ｉ薄膜を製造す
ることができる。 しかしながら、これらの値は、誘電
体薄膜としての実用化に充分な値ではなく、また、焼成
中にクラックが入り易い等の問題があった。On the other hand, the coating and firing method proposed by the present applicant is a solution method and can be fired at low temperatures, making it easy to control stoichiometry, and providing resistivity and insulation resistance equivalent to that of ceramic powder sintered bodies. A PbTiOi thin film having the following characteristics can be manufactured. However, these values are not sufficient for practical use as a dielectric thin film, and there are also problems such as easy cracking during firing.
このように、ＰｂＴｉＯｓ純組成では、実用的な良い特
性を持つ薄膜は得られていない。
′：本発明は、焼成中のクランク発生を
防止し、比抵抗、絶縁耐性を向上させた、実用に供しう
るＰｂＴｉ０゜＠誘電体薄膜を提供することを目的とす
る。As described above, a thin film with good practical properties cannot be obtained with a pure PbTiOs composition.
': An object of the present invention is to provide a practically usable PbTi0°@ dielectric thin film that prevents cranking during firing and has improved specific resistance and insulation resistance.
本発明は、組成式〔１〕
（１−（ｘ＋ｙ＋ｚ）） ＰｂＴｉＯ３＋ｘＭｎＯｔ＋
ｙＬａｚＯｓ＋ｚＳｉＯｚ ・＝ （１）
ｉ、：（ただし、Ｘ＋ｙおよび２は、０〜０．０１
であり、かつ、 χ＋ｙ＋ｚは、０．００１〜０．０１
である。）で表される組成を有するチタン酸鉛強誘電体
薄膜および塗布焼成法による該強誘電体ｆ！膜の製造方
法である。The present invention has a compositional formula [1] (1-(x+y+z)) PbTiO3+xMnOt+
yLazOs+zSiOz ・= (1)
i, :(However, X+y and 2 are 0 to 0.01
and χ+y+z is 0.001 to 0.01
It is. ) A lead titanate ferroelectric thin film having a composition expressed by the following and the ferroelectric material f! This is a method for manufacturing a membrane.
本発明において、強誘電体薄膜は、Ｍｎ０ｚ、ＬａｚＯ
ｉおよびＳｉＯ□よりなる群から選ばれた少なくとも１
種の金属酸化物を含有する前記組成式〔１〕で表される
組成を有するＰｂＴｉ０ｎＩ！膜である。In the present invention, the ferroelectric thin film is made of MnOz, LazO
At least one selected from the group consisting of i and SiO□
PbTiOnI! having the composition represented by the above compositional formula [1] containing a seed metal oxide! It is a membrane.
Ｍｎ０ｚ＋ Ｌａｇ’ｓまたは５ｉ（ｈを単独で含有す
る場合、組成式〔１〕中のＸ＋ Ｖまたは２は、０．０
０１以上であり、それらの２種以上を含有する場合には
、Ｘまたはｙば、０．０００５以上であることが好まし
い。 ただし、ｘ、 ｙおよび２の合計（＝ｘ＋ｙ＋ｚ
）は、０．Ｏ１以下である。Mn0z+ Lag's or 5i (when h is contained alone, X+ V or 2 in compositional formula [1] is 0.0
01 or more, and when two or more thereof are contained, it is preferable that X or y be 0.0005 or more. However, the sum of x, y and 2 (=x+y+z
) is 0. It is below O1.
該薄膜は、通常、耐熱性基板上、特に、電極として使用
可能な導電性金属酸化物、金属等の基板上に多層形成さ
れたミクロン・オーダーの膜厚の、導通のない、すなわ
ち、クラック、ピンホール等の欠陥のない、かつ、誘電
体として実用可能な緒特性値を有する薄膜である。The thin film is usually formed in multiple layers on a heat-resistant substrate, especially a conductive metal oxide, metal, etc. substrate that can be used as an electrode, and has a film thickness on the order of microns and has no conduction, that is, cracks. The thin film is free from defects such as pinholes and has properties that can be used practically as a dielectric.
本発明において、強誘電体薄膜は、加熱焼成により、前
記組成式〔１〕で表される組成を有する酸化物を生成す
る前駆体化合物または混合物の溶液を、耐熱性基板表面
に一様な厚さに塗布し、加熱焼成することにより製造す
る。In the present invention, the ferroelectric thin film is produced by applying a solution of a precursor compound or mixture that produces an oxide having the composition represented by the above composition formula [1] by heating and baking to a uniform thickness on the surface of a heat-resistant substrate. Manufactured by applying it to the surface and heating and baking it.
該製造方法において、原料として、有機溶剤溶解性の当
該金属化合物、たとえば、アルコキシド類、
）□士
カルボン酸塩類、キレート錯体、硝酸塩類等の混合溶液
またはそれらを反応させた前駆体化合物の溶液を使用す
ることができる。
Ｉ前駆体化合物または混合物溶液の、耐熱性基
板へ １゛の塗布法は、均一な厚さの
塗膜の得られる方法であ′］
れば、特に制限はない。 たとえば、ディッピング
１）ゴ
法、スプレー法、スピンナー法、刷毛塗り法等を採
トＴ、４ｔ４．：、Ａ；６ｆ＠４゜
ｉＧ １Ｍ ４″（Ｅ合
５１″混合’ＩｍＯ塗＠、に、ｌ’ｌＪＵ２ｍ成
。In the production method, the metal compound soluble in an organic solvent, such as alkoxides, as a raw material,
) A mixed solution of carboxylic acid salts, chelate complexes, nitrates, etc. or a solution of a precursor compound obtained by reacting them can be used.
There is no particular restriction on the method of applying the I precursor compound or mixture solution to the heat-resistant substrate as long as it is a method that provides a coating film of uniform thickness. For example, dipping
1) Adopt the Go method, spray method, spinner method, brush coating method, etc.
T, 4t4. :, A; 6f@4゜
iG 1M 4″ (E combination 51″ mixed 'ImO coating @, l'lJU2m composition
.
を繰９返６・所望０膜厚″■体薄膜２製造ｔ６・
、ｊ。Repeat 9 times 6. Desired 0 film thickness''■ body thin film 2 production t6.
,j.
〔作 用〕））
本発明において、ＰｂＴｉＯ３薄膜に存在する前記金属
酸化物は、薄膜欠陥、特に、加熱焼成時に発生し易いク
ランクの発生を防止し、欠陥のない良好なＰｂＴｌ１ｌ
ｌｌ：０３薄膜を形成する。[Function])) In the present invention, the metal oxide present in the PbTiO3 thin film prevents the occurrence of thin film defects, especially cranks that are likely to occur during heating and firing, and forms a good PbTiO3 film with no defects.
ll:03 Form a thin film.
さらに、ＭｎＯ□の存在は、ＰｂＴｉ０ｚ″ＴＲ膜の主
として比抵抗・絶縁耐圧を向上し・ま７・１°・０・０
存在は・ ｌ該薄膜の主として誘電損
失を低下させる。 １また
、５ｉｎ２の存在は、加熱焼成時のクランク発生の防止
効果が大きい。Furthermore, the presence of MnO□ mainly improves the resistivity and dielectric strength of the PbTi0z''TR film.
The presence of l reduces mainly the dielectric loss of the thin film. 1. Also, the presence of 5in2 has a great effect in preventing the occurrence of cranks during heating and firing.
したがって、前記金属酸化物は、目的に応してそれぞれ
が単独で存在してもよく、また、２種以上が存在しても
よい。Therefore, each of the metal oxides may be present alone, or two or more types may be present depending on the purpose.
これらの効果は、−１’ＩＱ式〔１〕中の（ｘ＋ｙ＋ｚ
）の値が、０．００１あれば発現する。These effects are expressed by (x+y+z
) is 0.001.
一方、その値が、０．０１を越えると、ＰｂＴｉＯｓと
しての誘電体特性が低下する。On the other hand, if the value exceeds 0.01, the dielectric properties of PbTiOs deteriorate.
すなわち、前記金属酸化物の１種を含有させる場合は、
Ｘ＋ Ｖまたは２の値を０．００１以上とするが、２種
以上を含有させる場合には、それらの合計量で０．００
１以上とすればよく、この場合、におよび／またはｙの
値が０．０００５以上であれば、前記Ｍｎ０ｚおよびＬ
ａ、Ｏ，に特有の効果が発現する。That is, when containing one type of metal oxide,
The value of X + V or 2 shall be 0.001 or more, but if two or more types are contained, the total amount of them shall be 0.001 or more.
It may be 1 or more; in this case, if the value of and/or y is 0.0005 or more, the Mn0z and L
A specific effect is expressed in a, O,.
本発明において、前些した如＜ 、ＰｂＴｉ０ｚの製造
方法として塗布焼成法を採用する。In the present invention, as mentioned above, a coating and firing method is employed as a method for producing PbTiOz.
塗布焼成法においては、ストイッキオメトリ制御が容易
であり、化学量論的な組成のＰｂＴｉＯｓ薄膜が得られ
る。In the coating and firing method, stoichiometric control is easy and a PbTiOs thin film with a stoichiometric composition can be obtained.
また、該方法において、原料溶液の塗布、焼成を繰り返
して薄膜を形成するが、繰り返しのない１回の塗布、焼
成では、極めて膜厚の薄いものしか得られず、また、厚
膜を得ようとすれば、クランク、ピンホール等の薄膜欠
陥を生じる。In addition, in this method, a thin film is formed by repeating the application and firing of the raw material solution, but a single application and firing without repetition can only yield an extremely thin film, and it is difficult to obtain a thick film. If so, thin film defects such as cranks and pinholes will occur.
したがって、塗布、焼成の繰り返しにより、所望の膜厚
の薄膜が得られ、薄膜層を積み重ねることにより、各画
ａＮに存在する欠陥が補修される。Therefore, by repeating coating and baking, a thin film with a desired thickness can be obtained, and by stacking the thin film layers, defects present in each image aN can be repaired.
本発明を、実施例をにより、さらに詳細に説明する。 The present invention will be explained in more detail with reference to Examples.
ただし、本発明の範囲は、下記実施例により、開環限定
されるものではない。However, the scope of the present invention is not limited to ring opening by the following examples.
（１）前駆体溶液の調製
当モルの酸化鉛： ｐｂｏおよびテトラブトキシチタン
：Ｔｒ（ＯＣ＊Ｈｑ）ａをアセチルアセトンに溶解し、
さらに、マンガンアセチルアセトナート：Ｍｎ（Ｏ＾ｃ
Ａｃ） ｚ、酢酸ランタン：Ｌａ（ＯＡｃ）ｓおよび／
またはテトラエトキシシラン：Ｓｉ （ＯＣｔＨｓ）
ａの所定量を添加し、８０〜９０℃の温度に加熱して反
応させ、金属酸化物換算濃度が、７，５χの均一な前駆
体溶液を調製した。(1) Preparation of precursor solution Equivalent moles of lead oxide: pbo and tetrabutoxytitanium: Tr(OC*Hq)a are dissolved in acetylacetone,
Furthermore, manganese acetylacetonate: Mn(O^c
Ac) z, lanthanum acetate: La(OAc)s and/
or tetraethoxysilane: Si (OCtHs)
A predetermined amount of a was added, and the mixture was heated to a temperature of 80 to 90°C to react, thereby preparing a uniform precursor solution having a metal oxide equivalent concentration of 7.5χ.
この前駆体溶液を加熱焼成して得られる組成物中のＭｎ
０ｔ＋Ｌａｚ０２および５ｉｆｔのモル比、Ｘ＋ ｙお
よび２の値を、第１表中に示す。Mn in the composition obtained by heating and baking this precursor solution
The molar ratios of 0t+Laz02 and 5ift, the values of X+y and 2 are shown in Table 1.
＋２） ＰｂＴｉＯ３薄膜強誘電体の製造２０００人
のＩＴＯ（スズをドープした酸化インジウム）膜をコー
トしたパイレックスガラス板または白金板に、前記調製
した前駆体溶液をスピンナー法またはディッピング法に
より一様な厚さに塗布して乾燥した後、電気炉中で５５
０℃の温度に２０ ｍＩｎ保持して加熱焼成した。+2) Manufacture of PbTiO3 thin film ferroelectric The precursor solution prepared above was applied to a Pyrex glass plate or platinum plate coated with 2000 ITO (tin-doped indium oxide) films to a uniform thickness by a spinner method or a dipping method. After coating and drying, it was heated in an electric oven for 55 minutes.
It was heated and fired at a temperature of 0° C. for 20 mIn.
前記前駆体溶液の塗布、乾燥および加熱焼成を繰り返し
、ＰｂＴｉ０＋の透明な薄膜体を得た。Application of the precursor solution, drying, and heating and baking were repeated to obtain a transparent thin film body of PbTi0+.
（３） 電気特性の測定
電気特性測定のため、得られたＰｂＴｉ０．薄膜の表面
に・ ２１Ｉｌ１１１×２１の金電極をスパッタリング
法により形成した。(3) Measurement of electrical properties To measure electrical properties, the obtained PbTi0. A gold electrode of 21Il111×21 was formed on the surface of the thin film by sputtering.
ついで、下記の諸電気特性を測定した。Then, the following electrical properties were measured.
比誘電率：ε 誘電損失： ｔａｎδ 比抵抗 ：ρ 絶縁耐圧：Ｅ飄、。。Relative permittivity: ε Dielectric loss: tanδ Specific resistance: ρ Dielectric strength: E,. .
残留分極：Ｐｒ 焦電係数：ｄＰｒ／ｄＴ （１００
ＫＶ／ａｍ直流、１００℃、１０分印加
諸電気特性の測定結果を、第１表中に示す。Residual polarization: Pr Pyroelectric coefficient: dPr/dT (100
Table 1 shows the measurement results of various electrical characteristics when applying KV/am direct current at 100° C. for 10 minutes.
また、比較として、前記方法と同様の方法で製造したＰ
ｂＴｉＯｓ純組成の薄膜について測定した電気特性値を
、第１表中に示す。In addition, for comparison, P produced using the same method as above
Table 1 shows the electrical property values measured for thin films of pure bTiOs composition.
本発明において、実施例の結果を示す第１表に示す如く
、ＭｎＯ□の存在は、比抵抗、絶縁耐圧および容積抵抗
積を向上させる効果が大きい。In the present invention, as shown in Table 1 showing the results of Examples, the presence of MnO□ has a large effect of improving specific resistance, dielectric strength voltage, and volume resistance area.
また、Ｌａ、Ｏ，の存在は、比抵抗および絶縁耐圧を向
上させる効果も有するが、特に誘電損失を低下させる効
果が大きい。Furthermore, the presence of La, O, has the effect of improving resistivity and dielectric strength, and has a particularly large effect of reducing dielectric loss.
Ｓｉｎｇの効果は、第１表からは明らかではないが、Ｓ
ｉＯ□の存在により、クランク等の薄膜欠陥のないチタ
ン酸鉛薄膜を得ることができる。Although the effect of Sing is not clear from Table 1,
Due to the presence of iO□, a lead titanate thin film without thin film defects such as cranks can be obtained.
本発明は、比抵抗および絶縁耐圧が大きく、誘電損失の
小さい、かつ、クランク等の薄膜欠陥の皆無な実用に供
しうる優れたチタン酸鉛強誘電体薄膜およびその製造方
法を提供するものであり、その産業的意義は極めて大き
い。The present invention provides an excellent lead titanate ferroelectric thin film that has high specific resistance and dielectric strength, low dielectric loss, and no thin film defects such as cranks, and can be used in practical applications, and a method for manufacturing the same. , its industrial significance is extremely large.
Claims (1)
＋ｙＬａ＿２Ｏ＿３＋ｚＳｉＯ＿２…〔１〕（ただし、
ｘ、ｙおよびｚは、０〜０．０１であり、かつ、ｘ＋ｙ
＋ｚは、０．００１〜０．０１である。）で表される組
成を有するチタン酸鉛強誘電体薄膜（２）加熱焼成によ
り、組成式 〔１−（ｘ＋ｙ＋ｚ）〕ＰｂＴｉＯ＿３＋ｘＭｎＯ＿２
＋ｙＬａ＿２Ｏ＿３＋ｚＳｉＯ＿２…〔１〕（ただし、
ｘ、ｙおよびｚは、０〜０．０１であり、かつ、ｘ＋ｙ
＋ｚは、０．００１〜０．０１である。）で表される組
成を有する酸化物を生成する前駆体化合物または混合物
の溶液を、耐熱性基板に塗布し、加熱焼成することを特
徴とするチタン酸鉛強誘電体薄膜の製造方法。(1) Composition formula [1-(x+y+z)]PbTiO_3+xMnO_2
+yLa_2O_3+zSiO_2...[1] (However,
x, y and z are 0 to 0.01, and x+y
+z is 0.001 to 0.01. ) Lead titanate ferroelectric thin film (2) By heating and baking, the composition formula [1-(x+y+z)]PbTiO_3+xMnO_2
+yLa_2O_3+zSiO_2...[1] (However,
x, y and z are 0 to 0.01, and x+y
+z is 0.001 to 0.01. 1. A method for producing a lead titanate ferroelectric thin film, which comprises applying a solution of a precursor compound or a mixture that produces an oxide having the composition represented by the following formula to a heat-resistant substrate, and heating and baking the solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12845685A JPS61285609A (en) | 1985-06-13 | 1985-06-13 | Lead titanate ferrodielectric thin film and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12845685A JPS61285609A (en) | 1985-06-13 | 1985-06-13 | Lead titanate ferrodielectric thin film and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61285609A true JPS61285609A (en) | 1986-12-16 |
| JPH0570242B2 JPH0570242B2 (en) | 1993-10-04 |
Family
ID=14985155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12845685A Granted JPS61285609A (en) | 1985-06-13 | 1985-06-13 | Lead titanate ferrodielectric thin film and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61285609A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63239150A (en) * | 1987-03-27 | 1988-10-05 | Sumitomo Electric Ind Ltd | Method for manufacturing superconducting ceramic thin films |
| JPH07211135A (en) * | 1993-12-01 | 1995-08-11 | Matsushita Electric Ind Co Ltd | Ferroelectric thin film and manufacturing method thereof |
| US5571495A (en) * | 1994-08-11 | 1996-11-05 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Dielectric thin film of substituted lead titanate |
| US5717157A (en) * | 1993-12-01 | 1998-02-10 | Matsushita Electric Industrial Co., Ltd. | Ferroelectric thin film and method of manufacturing the same |
| US6121647A (en) * | 1996-06-26 | 2000-09-19 | Tdk Corporation | Film structure, electronic device, recording medium, and process of preparing ferroelectric thin films |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138004A (en) * | 1983-01-27 | 1984-08-08 | 松下電器産業株式会社 | Ferrodielectric thin film |
| JPS59141427A (en) * | 1983-02-01 | 1984-08-14 | Matsushita Electric Ind Co Ltd | Thin film of ferroelectric material |
-
1985
- 1985-06-13 JP JP12845685A patent/JPS61285609A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138004A (en) * | 1983-01-27 | 1984-08-08 | 松下電器産業株式会社 | Ferrodielectric thin film |
| JPS59141427A (en) * | 1983-02-01 | 1984-08-14 | Matsushita Electric Ind Co Ltd | Thin film of ferroelectric material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63239150A (en) * | 1987-03-27 | 1988-10-05 | Sumitomo Electric Ind Ltd | Method for manufacturing superconducting ceramic thin films |
| JPH07211135A (en) * | 1993-12-01 | 1995-08-11 | Matsushita Electric Ind Co Ltd | Ferroelectric thin film and manufacturing method thereof |
| US5717157A (en) * | 1993-12-01 | 1998-02-10 | Matsushita Electric Industrial Co., Ltd. | Ferroelectric thin film and method of manufacturing the same |
| US5989395A (en) * | 1993-12-01 | 1999-11-23 | Matsushita Electric Industrial Co., Ltd. | Ferroelectric thin film and method of manufacturing the same |
| US5571495A (en) * | 1994-08-11 | 1996-11-05 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Dielectric thin film of substituted lead titanate |
| US6121647A (en) * | 1996-06-26 | 2000-09-19 | Tdk Corporation | Film structure, electronic device, recording medium, and process of preparing ferroelectric thin films |
| US6387712B1 (en) | 1996-06-26 | 2002-05-14 | Tdk Corporation | Process for preparing ferroelectric thin films |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570242B2 (en) | 1993-10-04 |
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