JPH0637329B2 - Method for producing lead titanate thin film - Google Patents
Method for producing lead titanate thin filmInfo
- Publication number
- JPH0637329B2 JPH0637329B2 JP2147249A JP14724990A JPH0637329B2 JP H0637329 B2 JPH0637329 B2 JP H0637329B2 JP 2147249 A JP2147249 A JP 2147249A JP 14724990 A JP14724990 A JP 14724990A JP H0637329 B2 JPH0637329 B2 JP H0637329B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- lead titanate
- titanate thin
- lead
- producing
- 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.)
- Expired - Lifetime
Links
- 239000010409 thin film Substances 0.000 title claims description 26
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005118 spray pyrolysis Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- -1 titanium alkoxide Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- VSFQMZYFJAOOOG-UHFFFAOYSA-N di(propan-2-yloxy)lead Chemical compound CC(C)O[Pb]OC(C)C VSFQMZYFJAOOOG-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- RCZPHVPIOWNERS-UHFFFAOYSA-N CCCO[Ti] Chemical compound CCCO[Ti] RCZPHVPIOWNERS-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XKENYNILAAWPFQ-UHFFFAOYSA-N dioxido(oxo)germane;lead(2+) Chemical compound [Pb+2].[O-][Ge]([O-])=O XKENYNILAAWPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
- Radiation Pyrometers (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は、赤外線検出材料であるチタン酸鉛薄膜の製造
方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a lead titanate thin film which is an infrared detection material.
(従来の技術) 一般に赤外線検出材料として代表的なものにはCdHgTe，
InSb及びSi等の半導体とチタン酸鉛、ゲルマン酸鉛、TG
S，PVF2等の焦電体とがある。前者は液体窒素で冷却し
て用いる必要があり、後者は冷却する必要がない。従っ
て、焦電体を用いた非冷却型の赤外線検出器は冷却型に
比べて性能面ではやや劣るものの、低価格、小型軽量及
び扱い易い等の特徴があるため、人体検知器や火災報知
器等に利用されており、今後ますます利用範囲が広がる
傾向にある。チタン酸鉛は、数多くある焦電材料のなか
で、薄膜化が容易であり、感度の良い赤外線検出材料と
して有望なものである。(Prior Art) CdHgTe is a typical infrared detection material,
Semiconductors such as InSb and Si and lead titanate, lead germanate, TG
There are pyroelectric materials such as S and PVF 2 . The former needs to be used after being cooled with liquid nitrogen, and the latter need not be cooled. Therefore, an uncooled infrared detector using a pyroelectric body is slightly inferior in performance to a cooled type, but it has features such as low cost, small size and light weight, and easy handling. It is used for various purposes, and the range of use tends to expand in the future. Lead titanate is a promising infrared detection material with high sensitivity because it can be easily formed into a thin film among many pyroelectric materials.
従来、チタン酸鉛薄膜はチタン及び鉛の各酸化物を混合
・焼結し、得られた素材を研磨することにより作られて
きた。しかし、一般にセラミックスはもろく、この方法
ではほぼ３０μｍ程度が厚さの限界であると共に加工工
程でのひび割れも多く、大きな面積の薄膜を得るのが困
難である。また、チタン酸鉛薄膜を得る他の方法とし
て、スパッタ法が用いられている。この方法は良質の薄
膜を作る技術として多くの電子材料に応用されている
が、焦電体薄膜の形成では成膜速度が１０〜２０Å／mi
nと非常に遅く、所定の厚さの膜を得るのに長時間を要
する。さらに、チタン酸鉛の薄膜を得る他の方法として
化学気相成長(ＣＶＤ)法が近年用いられてきたが、この
方法は成膜速度がスパッタ法に比べて１０〜２０倍と比
較的速く、かつ膜組成の制御も容易であるが、スパッタ
法同様、大掛かりな装置を必要とする点が問題である。Conventionally, a lead titanate thin film has been produced by mixing and sintering each oxide of titanium and lead, and polishing the obtained material. However, ceramics are generally fragile, and in this method, the thickness is limited to about 30 μm and many cracks are generated in the processing step, and it is difficult to obtain a thin film having a large area. A sputtering method is used as another method for obtaining a lead titanate thin film. This method has been applied to many electronic materials as a technique for producing good quality thin films, but in the formation of pyroelectric thin films, the deposition rate is 10 to 20Å / mi.
n is very slow, and it takes a long time to obtain a film having a predetermined thickness. Further, chemical vapor deposition (CVD) has been used in recent years as another method for obtaining a thin film of lead titanate. However, this method has a film formation rate that is 10 to 20 times faster than the sputtering method, Moreover, although the film composition can be easily controlled, the problem is that a large-scale apparatus is required as in the sputtering method.
(発明が解決しようとする課題) 従来のチタン酸鉛薄膜の製造方法は、スパッタ装置又は
ＣＶＤ装置など大掛かりな装置を必要とするうえ、成膜
に膨大な時間を要する等の欠点があった。(Problems to be Solved by the Invention) The conventional method for producing a lead titanate thin film has drawbacks that it requires a large-scale apparatus such as a sputtering apparatus or a CVD apparatus, and that it takes an enormous amount of time for film formation.
本発明は、上記のような問題点を解消するためになされ
たもので、簡単な装置を用い、短時間で、チタン酸鉛の
薄膜を得ることが可能なチタン酸鉛薄膜の製造方法を提
供することを目的とする。The present invention has been made to solve the above problems, and provides a method for producing a lead titanate thin film, which is capable of obtaining a lead titanate thin film in a short time using a simple device. The purpose is to do.
(課題を解決するための手段) 本発明では、原料に鉛のアルコキシドとチタンのアルコ
キシドとを用い、スプレーパイロリシス法によりチタン
酸鉛薄膜を製造する。(Means for Solving the Problem) In the present invention, a lead titanate thin film is produced by a spray pyrolysis method using lead alkoxide and titanium alkoxide as raw materials.
本発明におけるスプレーパイロリシス法によるチタン酸
鉛薄膜の製造手順は次のようになる。まず、出発原料と
して鉛のアルコキシド及びチタンのアルコキシドを用
い、各成分の金属アルコキシドを所定の成分比に混合す
る。次に、混合した原料溶液を加熱した基板上に吹き付
け非晶質焦電体薄膜を形成する。その後、電気炉等を用
いて熱処理を加えて焦電体薄膜を得る。The procedure for producing a lead titanate thin film by the spray pyrolysis method in the present invention is as follows. First, lead alkoxide and titanium alkoxide are used as starting materials, and the metal alkoxide of each component is mixed in a predetermined component ratio. Next, the mixed raw material solution is sprayed onto the heated substrate to form an amorphous pyroelectric thin film. Then, heat treatment is applied using an electric furnace or the like to obtain a pyroelectric thin film.
(作用) 上述のように、本発明では、原料として溶液を使用する
ため、(１)各成分が原子レベルで混合し均一な膜が得ら
れる。(２)膜組成が仕込みの成分比を調整するだけで簡
単に制御できる。(３)平板状の基板のみならず、多様な
形状の基板を用いることにより、自由なパターン形成が
可能である。(４)膜厚は吹き付けの回数と原料溶液の濃
度を調整することによって任意に設定することができる
等の利点がある。(Operation) As described above, in the present invention, since the solution is used as the raw material, (1) the components are mixed at the atomic level to obtain a uniform film. (2) The film composition can be easily controlled simply by adjusting the composition ratio of the charge. (3) It is possible to freely form patterns by using not only a flat plate-shaped substrate but also substrates having various shapes. (4) There is an advantage that the film thickness can be arbitrarily set by adjusting the number of times of spraying and the concentration of the raw material solution.
また、工業的には吹き付け装置と電気炉などの簡単な装
置により短時間の焼成で焦電特性をもつチタン酸鉛薄膜
の成膜が可能となり、極めて経済性の高い薄膜作成技術
である。Further, industrially, it is possible to form a lead titanate thin film having pyroelectric properties by a simple device such as a spraying device and an electric furnace in a short time, which is a very economical thin film forming technique.
さらに、スプレーパイロリシス法における出発原料とし
ては無機酸、有機酸、無機金属塩及び有機金属塩などが
あるが、これらの中で有機金属塩に含まれる金属アルコ
キシドは、高純度のものが得やすく、原子レベルで混合
できるので低温での成膜が可能であるなど他の金属塩に
比べて優れた点が多い。Further, as a starting material in the spray pyrolysis method, there are inorganic acids, organic acids, inorganic metal salts, organic metal salts, and the like. Among these, the metal alkoxide contained in the organic metal salt is easy to obtain in high purity. Since it can be mixed at the atomic level, it has many advantages over other metal salts such as low temperature film formation.
(発明の実施例) 第１図に本発明の実施例におけるチタン酸鉛薄膜の製造
工程のフローチャートを示す。以下順を追って本発明の
実施例を説明する。(Embodiment of the Invention) FIG. 1 shows a flowchart of a manufacturing process of a lead titanate thin film in an embodiment of the present invention. Examples of the present invention will be described below in order.
まず、混合工程１において各成分の金属アルコキシドを
所定の成分比に混合する。具体的には、金属アルコキシ
ドとして、ジ−イソ−プロポキシ鉛(Pb(O-i-C3H7)2)と
テトラ−イソ−プロポキシチタン(Ti(O-i-C3H7)4)を用
いる。なお、ジ−イソ−プロポキシ鉛は室温では固体の
ため、エタノールを溶媒としたジ−イソ−プロポキシ鉛
のエタノール溶液を用いる。これらの溶液をＰbとＴiの
モル比が１：１の化学量論的組成比になるように秤量し
混合する。First, in the mixing step 1, the metal alkoxide of each component is mixed in a predetermined component ratio. Specifically, as the metal alkoxide, di - iso - propoxy lead (Pb (OiC 3 H 7) 2) tetra - iso - using propoxytitanium (Ti (OiC 3 H 7) 4). Since di-iso-propoxy lead is a solid at room temperature, an ethanol solution of di-iso-propoxy lead in ethanol is used. These solutions are weighed and mixed so that the molar ratio of Pb and Ti becomes a stoichiometric composition ratio of 1: 1.
次に、スプレー工程２において混合溶液を基板に吹き付
け塗布する。吹き付けにはハンドスプレーを用い、５０
℃に加熱したアルミナ基板上に大気中で１回当たり０．
５μｍ程度堆積させ、乾燥工程３にて乾燥させる。これ
らの工程２，３は所定の膜厚になるまで繰り返す。次
に、焼成工程４において、この塗布した基板を電気炉を
用いて大気中で約６００〜１２００℃の範囲内の特定温
度で１０分間若しくはそれ以上加熱・焼成する。この結
果、結晶のＣ軸(基板面に垂直)に強く配向した焦電特性
をもつペロブスカイト構造のチタン酸鉛薄膜を得ること
ができる。Next, in a spray process 2, the mixed solution is sprayed and applied on the substrate. Hand spray is used for spraying, 50
On an alumina substrate heated to 0 ° C., in air at a time of 0.
It is deposited to a thickness of about 5 μm and dried in the drying step 3. These steps 2 and 3 are repeated until a predetermined film thickness is obtained. Next, in firing step 4, this coated substrate is heated and fired for 10 minutes or more at a specific temperature in the range of about 600 to 1200 ° C. in the atmosphere using an electric furnace. As a result, it is possible to obtain a lead titanate thin film having a perovskite structure having pyroelectric characteristics that is strongly oriented in the C axis of the crystal (perpendicular to the substrate surface).
なお、焼成温度が約６００℃よりも低い場合には基板上
に堆積した非晶質薄膜を充分結晶化させることができ
ず、また約１２００℃より高いとチタン酸鉛が溶融状態
となってしまうので好ましくない。If the baking temperature is lower than about 600 ° C., the amorphous thin film deposited on the substrate cannot be sufficiently crystallized, and if it is higher than about 1200 ° C., lead titanate will be in a molten state. It is not preferable.
また、基板はアルミナ以外の耐熱材を採用することもで
きる。Further, the substrate may be made of a heat resistant material other than alumina.
(発明の効果) 以上のように、本発明のチタン酸鉛薄膜の製造方法によ
れば、出発材料に各成分の金属アルコキシドを用い、か
つスプレーパイロリシス法を採用したので、製造装置が
簡単であり、かつ短時間でチタン酸鉛薄膜が得られる効
果がある。(Effects of the Invention) As described above, according to the method for producing a lead titanate thin film of the present invention, the metal alkoxide of each component is used as the starting material, and the spray pyrolysis method is adopted. There is an effect that a lead titanate thin film can be obtained in a short time.
第１図は本発明の一実施例に係るチタン酸鉛薄膜の作製
フローチャートである。 １……混合工程、２……スプレー工程、３……乾燥工
程、４……焼成工程。FIG. 1 is a flow chart for producing a lead titanate thin film according to an embodiment of the present invention. 1 ... Mixing process, 2 ... Spraying process, 3 ... Drying process, 4 ... Firing process.
Claims (1)
ルコキシドとを用い、スプレーパイロリシス法によりチ
タン酸鉛薄膜を作成することを特徴とするチタン酸鉛薄
膜の製造方法。1. A method for producing a lead titanate thin film, characterized in that a lead titanate thin film is prepared by a spray pyrolysis method using lead alkoxide and titanium alkoxide as raw materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2147249A JPH0637329B2 (en) | 1990-06-07 | 1990-06-07 | Method for producing lead titanate thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2147249A JPH0637329B2 (en) | 1990-06-07 | 1990-06-07 | Method for producing lead titanate thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0442856A JPH0442856A (en) | 1992-02-13 |
| JPH0637329B2 true JPH0637329B2 (en) | 1994-05-18 |
Family
ID=15425961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2147249A Expired - Lifetime JPH0637329B2 (en) | 1990-06-07 | 1990-06-07 | Method for producing lead titanate thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637329B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019225696A1 (en) * | 2018-05-25 | 2019-11-28 | コニカミノルタ株式会社 | Molecular transformation member, layered body, and method for modifying substrate |
-
1990
- 1990-06-07 JP JP2147249A patent/JPH0637329B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0442856A (en) | 1992-02-13 |
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