JPH08133734A - Dielectric crystal film - Google Patents
Dielectric crystal filmInfo
- Publication number
- JPH08133734A JPH08133734A JP6271266A JP27126694A JPH08133734A JP H08133734 A JPH08133734 A JP H08133734A JP 6271266 A JP6271266 A JP 6271266A JP 27126694 A JP27126694 A JP 27126694A JP H08133734 A JPH08133734 A JP H08133734A
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- JP
- Japan
- Prior art keywords
- substrate
- film
- crystal film
- mmol
- aqueous solution
- 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.)
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- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、圧電アクチュエータ、
圧電センサ、焦電センサ、誘電体素子等に使用すること
ができる、誘電体結晶膜に関するものである。FIELD OF THE INVENTION The present invention relates to a piezoelectric actuator,
The present invention relates to a dielectric crystal film that can be used for a piezoelectric sensor, a pyroelectric sensor, a dielectric element and the like.
【0002】[0002]
【従来技術及びその問題点】誘電体結晶膜は、上記のよ
うに電子材料として幅広い応用分野を有する。特に、強
誘電体であるPb(ZrTi)O3 系材料は、その置換
や添加物の効果も含め種々検討されている。しかしなが
ら、これまでに実用化されているセラミックス材料は、
キュリー温度が200〜400℃であり、このため、半
田付けに伴う温度上昇による性能劣化が問題となってい
た。例えば、焦電体材料として使用されている(PbC
a)TiO3 系ペロブスカイト材料において、焦電係数
が3.5×10-8[C/cm2 ・K]と大きく性能の良
い組成では、キュリー温度は250℃程度と低い。一
方、薄膜化による性能向上が試みられているが、従来の
方法では、成膜後の結晶化のための熱処理、あるいは成
膜時に高温に保ことが必要であり、600℃程度の熱処
理工程を避けることができない。このため、熱処理工程
時において強誘電体結晶膜材料との相互拡散のない基板
を選ぶと共に、強誘電体薄膜材料にクラックが入るのを
防ぐために、基板として強誘電体薄膜材料と同程度の熱
膨張係数を有する基板を選択する必要があるという問題
点があった。2. Description of the Related Art As mentioned above, dielectric crystal films have a wide range of applications as electronic materials. In particular, various studies have been conducted on the Pb (ZrTi) O 3 -based material, which is a ferroelectric substance, including the effects of its substitution and additives. However, the ceramic materials that have been practically used so far are
The Curie temperature is 200 to 400 [deg.] C. Therefore, there has been a problem of performance deterioration due to temperature rise associated with soldering. For example, it is used as a pyroelectric material (PbC
a) In the TiO 3 -based perovskite material, the composition having a large pyroelectric coefficient of 3.5 × 10 −8 [C / cm 2 · K] and good performance has a low Curie temperature of about 250 ° C. On the other hand, performance improvement by thinning the film has been attempted, but in the conventional method, it is necessary to perform heat treatment for crystallization after film formation, or to keep it at a high temperature during film formation. I can't avoid it. For this reason, a substrate that does not interdiffuse with the ferroelectric crystal film material during the heat treatment process is selected, and in order to prevent cracks from occurring in the ferroelectric thin film material, the substrate is treated with the same heat as the ferroelectric thin film material. There is a problem that it is necessary to select a substrate having a coefficient of expansion.
【0003】[0003]
【本発明の目的】本発明は、上記問題点を解決するため
になされたものであり、低温プロセスで成膜可能であ
り、またキュリー温度の高いPb(ZrTi)O3 系材
料を提供することを目的とする。An object of the present invention is to solve the above problems, and to provide a Pb (ZrTi) O 3 -based material which can be formed into a film by a low temperature process and has a high Curie temperature. With the goal.
【0004】[0004]
【問題点を解決するための手段】本発明は、水熱合成に
より基板上に形成したPb(Zrx Ti1-x )O3 (た
だし、0≦x≦1である。)からなる誘電体結晶膜にお
いて、Pbに対して20原子%以下のKを含有すること
を特徴とする誘電体結晶膜に関する。According to the present invention, a dielectric material of Pb (Zr x Ti 1-x ) O 3 (where 0 ≦ x ≦ 1) is formed on a substrate by hydrothermal synthesis. The present invention relates to a dielectric crystal film containing K in an amount of 20 atomic% or less with respect to Pb in the crystal film.
【0005】本発明に使用される基板としては、金属
板、表面を酸化処理した金属板、および金属コーティン
グされた樹脂基板又は絶縁体基板等を挙げることができ
る。金属板としては、チタン基板、ステンレス、Fe−
Ni合金等が用いられる。また、樹脂基板としては、ポ
リイミドフィルムやポリフェニレンサルファイド等の耐
熱性の樹脂基板が好ましい。コーティング用金属として
はPt、Ti等が用いられる。Examples of the substrate used in the present invention include a metal plate, a metal plate whose surface is oxidized, and a resin substrate or an insulating substrate coated with a metal. As the metal plate, a titanium substrate, stainless steel, Fe-
Ni alloy or the like is used. Further, as the resin substrate, a heat resistant resin substrate such as a polyimide film or polyphenylene sulfide is preferable. Pt, Ti, or the like is used as the coating metal.
【0006】本発明において、基板として1〜100μ
mの厚さのチタン金属箔等の金属基板を使用し、50μ
m以下、好ましくは10μm以下の厚さの強誘電体結晶
膜を水熱合成法等により基板上に形成した場合には、特
に絶縁抵抗が高く、誘電損失の小さい強誘電体結晶膜を
得ることができる。In the present invention, the substrate is 1 to 100 μm.
Using a metal substrate such as titanium metal foil with a thickness of m, 50μ
When a ferroelectric crystal film having a thickness of m or less, preferably 10 μm or less is formed on a substrate by a hydrothermal synthesis method or the like, a ferroelectric crystal film having particularly high insulation resistance and small dielectric loss is obtained. You can
【0007】本発明の強誘電体結晶膜層を基板上に形成
する方法について詳述する。基板として、Ti基板ある
いはTiをコーティングした基板を選択し、前記基板上
に水熱合成によって強誘電体結晶膜を作製する。また、
強誘電体結晶膜を水熱法により形成する際に使用される
Pb、Zr、Ti構成元素を含有する原料化合物として
は、塩化物、オキシ塩化物、硝酸塩、アルコキシド、酢
酸塩、水酸化物、酸化物等が好ましい。この強誘電体結
晶膜の形成は以下のようにして行う。The method of forming the ferroelectric crystal film layer of the present invention on the substrate will be described in detail. A Ti substrate or a substrate coated with Ti is selected as a substrate, and a ferroelectric crystal film is formed on the substrate by hydrothermal synthesis. Also,
As the raw material compound containing Pb, Zr, and Ti constituent elements used when forming the ferroelectric crystal film by the hydrothermal method, chloride, oxychloride, nitrate, alkoxide, acetate, hydroxide, Oxides and the like are preferable. This ferroelectric crystal film is formed as follows.
【0008】まずPb(NO3 )2 水溶液50mmol/l〜
500mmol/l、ZrOCl2 水溶液20mmol/l〜500
mmol/l、TiCl4 水溶液0.002mmol/l〜50mmol
/lおよびKOH水溶液1mol/l 〜8mol/l の混合溶液中
に、前記基板を投入し、140〜190℃の温度で、6
〜24時間水熱による表面処理を行い、Pb(ZrXT
i1-X )O3 (0≦x≦1)からなる結晶核を形成す
る。結晶核形成時にTi含有原料化合物を存在させて水
熱反応を行った後、成長反応を行うことにより配向性の
高い強誘電体結晶膜が得られる。First, a Pb (NO 3 ) 2 aqueous solution of 50 mmol / l
500 mmol / l, ZrOCl 2 aqueous solution 20 mmol / l-500
mmol / l, TiCl 4 aqueous solution 0.002 mmol / l to 50 mmol
/ l and KOH aqueous solution 1mol / l ~ 8mol / l into the mixed solution of the substrate, at a temperature of 140 ~ 190 ℃, 6
Approximately 24 hours hydrothermal surface treatment, Pb (Zr X T
i 1−X ) O 3 (0 ≦ x ≦ 1) form a crystal nucleus. A ferroelectric crystal film having a high orientation is obtained by allowing a Ti-containing starting compound to be present in the formation of crystal nuclei to carry out a hydrothermal reaction and then carrying out a growth reaction.
【0009】次に結晶を成長させるため、Pb(N
O3 )2 水溶液50mmol/l〜500mmol/l、ZrOCl
2 水溶液10mmol/l〜500mmol/l、TiCl4 水溶液
5mmol/l〜400mmol/lおよびKOH水溶液2mol/l 〜
8mol/l の混合溶液中に、前記結晶核が形成された基板
を投入して150〜200℃、1〜24時間水熱処理
し、急速な結晶化を行う。これにより基板上に強誘電体
結晶膜が形成される。水熱処理における加熱方法は油浴
や電気炉などによる。その後一般的な洗浄を行う。例え
ば、純水中で超音波洗浄を行い、ついで酢酸水溶液中で
超音波洗浄を行った後、純水中で超音波洗浄を行い、1
00〜120℃で12時間程度乾燥させる。このように
して形成された誘電体結晶膜の組成は、Pbに対して2
0原子%以下のKを含有する。Next, in order to grow a crystal, Pb (N
O 3 ) 2 aqueous solution 50 mmol / l to 500 mmol / l, ZrOCl
2 aqueous solution 10 mmol / l to 500 mmol / l, TiCl 4 aqueous solution 5 mmol / l to 400 mmol / l and KOH aqueous solution 2 mol / l
The substrate on which the crystal nuclei are formed is placed in a mixed solution of 8 mol / l and subjected to hydrothermal treatment at 150 to 200 ° C. for 1 to 24 hours to perform rapid crystallization. As a result, a ferroelectric crystal film is formed on the substrate. The heating method in the hydrothermal treatment is an oil bath or an electric furnace. After that, general cleaning is performed. For example, ultrasonic cleaning is performed in pure water, then ultrasonic cleaning in an acetic acid aqueous solution, and then ultrasonic cleaning in pure water.
It is dried at 00 to 120 ° C. for about 12 hours. The composition of the dielectric crystal film thus formed is 2 with respect to Pb.
It contains 0 atomic% or less of K.
【0010】水熱反応による結晶核の形成をレイノルズ
数が2000以下、好ましくは1000以下の条件で行
い、ついで結晶させることにより配向性がさらに優れた
強誘電体薄膜が得られる。なお、結晶成長させる際の形
成条件としては層流下でも乱流下でもよいが、適度に攪
拌することにより成膜速度を大きくすることができる。Formation of crystal nuclei by hydrothermal reaction is performed under conditions of Reynolds number of 2000 or less, preferably 1000 or less, followed by crystallization to obtain a ferroelectric thin film having further excellent orientation. The conditions for crystal growth may be laminar flow or turbulent flow, but the film formation rate can be increased by appropriate stirring.
【0011】本発明で得られる強誘電体結晶膜を素子化
する場合に使用される電極としては、特に限定されない
がコストや量産性を考慮し最適なものが選定される。例
えば、スパッタリング法によるNi、無電解メッキ法に
よるNi、焼付けタイプのAg等が選択使用される。そ
の他、蒸着によるAl、スパッタリング法によるPtあ
るいはAu等も用いられる。なお、基板に樹脂を用いる
場合には、高温に加熱できないので焼付けタイプのAg
電極は好ましくない。The electrode used when the ferroelectric crystal film obtained in the present invention is formed into an element is not particularly limited, but an optimum electrode is selected in consideration of cost and mass productivity. For example, Ni by the sputtering method, Ni by the electroless plating method, baking type Ag, etc. are selectively used. In addition, Al by vapor deposition, Pt or Au by sputtering method, etc. are also used. In addition, when resin is used for the substrate, it cannot be heated to high temperature, so baking type Ag is used.
Electrodes are not preferred.
【0012】[0012]
【実施例】以下、本発明の具体的実施例についてさらに
詳細に説明する。EXAMPLES Hereinafter, specific examples of the present invention will be described in more detail.
【0013】実施例1 Pb(NO3 )2 水溶液16mmol、ZrOCl2 水溶液
8mmol、TiCl4 水溶液0.08mmolおよびKOH水
溶液0.3 molの混合溶液(溶液合計量150ml)中
に、Ti基板を設置固定し、180℃で12時間の水熱
処理を行いPb(ZrTi)O3 の結晶核を生成させ
た。次に、結晶成長のためPb(NO3 ) 2 水溶液16
mmol、ZrOCl2 水溶液8.32mmol、TiCl4 水
溶液7.68mmolおよびKOH水溶液2.24 molの混
合溶液(溶液合計量640ml)中に投入し、160
℃、10時間の水熱処理を行ってKを含有するPb(Z
rTi)O3 の膜を形成した。その後、純水中での超音
波洗浄3分間×2回、1mol/l酢酸水溶液中で超音波洗
浄3分間×2回、およびさらに純水中で超音波洗浄3分
間×2回を行い、100℃で12時間乾燥を行った。こ
のようにして得られた結晶膜のX線回折パターンを図1
に、また、ICP、EPMA等によって確認された膜中
のK濃度は、Pbに対して10原子%であった。このよ
うにして作製したPb(ZrX Ti1-X )O3 (ただ
し、xは0.52である。)膜は、分極処理を施さなく
ても分極軸が揃っており、500℃の熱処理を施した後
も焦電係数は3.0×10-8[C/cm2 ・K]で変化
なく、キュリー温度が500℃以上であることが確認さ
れた。Example 1 Pb (NO3)216 mmol aqueous solution, ZrOCl2Aqueous solution
8 mmol, TiClFour0.08 mmol aqueous solution and KOH water
Solution 0.3 mol in a mixed solution (total solution volume 150 ml)
Install and fix the Ti substrate at 180 ° C for 12 hours with hydrothermal heat.
Treated with Pb (ZrTi) O3To generate crystal nuclei of
Was. Next, Pb (NO3) 2Aqueous solution 16
mmol, ZrOCl2Aqueous solution 8.32mmol, TiClFourwater
A mixture of 7.68 mmol solution and 2.24 mol KOH aqueous solution
Pour into the combined solution (total solution volume 640 ml) and
Pb (Z containing K after hydrothermal treatment at 10 ° C for 10 hours
rTi) O3Was formed. Then, the super sound in pure water
Wave cleaning 3 minutes × 2 times, ultrasonic cleaning in 1 mol / l acetic acid aqueous solution
Purification 3 minutes x 2 times, and further ultrasonic cleaning in pure water 3 minutes
The drying was performed for 12 hours at 100 ° C. for 2 times. This
Fig. 1 shows the X-ray diffraction pattern of the crystalline film obtained in the above manner.
In addition, in the film confirmed by ICP, EPMA, etc.
The K concentration of was 10 atomic% with respect to Pb. This
Thus prepared Pb (ZrXTi1-X) O3(However
However, x is 0.52. ) The membrane is not polarized
Even though the polarization axes are uniform, after heat treatment at 500 ° C
Pyroelectric coefficient is 3.0 × 10-8[C / cm2・ K] changes
And the Curie temperature is not less than 500 ° C.
It was
【0014】実施例2 次に、実施例1と同様な方法により結晶核を形成させた
後、結晶成長のためPb(NO3 )2 水溶液16mmol、
ZrOCl2 水溶液8.32mmol、TiCl4水溶液
7.68mmolおよびKOH水溶液2.56 molの混合溶
液(溶液合計量640ml)中に投入し、190℃、2
時間の水熱条件でPb(ZrTi)O3 の膜を形成し
た。その後、実施例1と同様な洗浄を行った。このよう
にして得られた結晶膜のX線回折パターンを図2に、ま
た、ICP、EPMA等によって確認された膜中のK濃
度は、Pbに対して15原子%であった。このようにし
て作製したPb(ZrX Ti1-X )O3 (ただし、xは
0.52である。)膜は、分極処理を施さなくても分極
軸が揃っており、500℃の熱処理を施した後も焦電係
数は2.5×10-8[C/cm2 ・K]で変化なく、キ
ュリー温度が500℃以上であることが確認された。Example 2 Next, after forming crystal nuclei by the same method as in Example 1, 16 mmol of an aqueous Pb (NO 3 ) 2 solution for crystal growth,
A ZrOCl 2 aqueous solution (8.32 mmol), a TiCl 4 aqueous solution (7.68 mmol) and a KOH aqueous solution (2.56 mol) were put into a mixed solution (total amount of solution: 640 ml), and the mixture was heated at 190 ° C. for 2 hours.
A film of Pb (ZrTi) O 3 was formed under hydrothermal conditions for an hour. Then, the same washing as in Example 1 was performed. The X-ray diffraction pattern of the crystalline film thus obtained is shown in FIG. 2, and the K concentration in the film confirmed by ICP, EPMA, etc. was 15 atomic% with respect to Pb. The Pb (Zr x Ti 1-x ) O 3 (where x is 0.52) film thus prepared has the same polarization axis even if polarization treatment is not performed, and the heat treatment at 500 ° C. It was confirmed that the Curie temperature was 500 ° C. or higher without changing the pyroelectric coefficient at 2.5 × 10 −8 [C / cm 2 · K] even after the treatment.
【0015】[0015]
【発明の効果】以上のように、水熱合成によって形成さ
れた、Pbに対して20原子%以下のKを含有するPb
(ZrTi)O3 系の誘電体結晶膜は、分極処理を施さ
なくても分極軸が揃っており、そのキュリー温度は50
0℃以上と高いので半田付け時等における特性劣化がな
い。Industrial Applicability As described above, Pb formed by hydrothermal synthesis and containing 20 atomic% or less of K relative to Pb.
The (ZrTi) O 3 -based dielectric crystal film has a uniform polarization axis even if it is not subjected to polarization treatment, and its Curie temperature is 50.
Since the temperature is as high as 0 ° C. or higher, there is no characteristic deterioration during soldering.
【図1】本発明により得られる結晶成長反応後のPb
(ZrTi)O3 配向性結晶膜のX線回折パターンを示
す図である。FIG. 1 Pb after a crystal growth reaction obtained by the present invention
Is a diagram showing an X-ray diffraction pattern of (ZrTi) O 3 oriented crystalline film.
【図2】本発明により得られる結晶成長反応後のPb
(ZrTi)O3 配向性結晶膜のX線回折パターンを示
す図である。FIG. 2 Pb after the crystal growth reaction obtained by the present invention
Is a diagram showing an X-ray diffraction pattern of (ZrTi) O 3 oriented crystalline film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 H01L 41/187 (72)発明者 木村 隆幸 山口県宇部市大字小串1978番地の5 宇部 興産株式会社宇部研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location H01L 41/187 (72) Inventor Takayuki Kimura 5 1978 at Kogushi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Ube Institute
Claims (1)
(Zrx Ti1-x )O 3 (ただし、0≦x≦1であ
る。)からなる誘電体結晶膜において、Pbに対して2
0原子%以下のKを含有することを特徴とする誘電体結
晶膜。1. Pb formed on a substrate by hydrothermal synthesis
(ZrxTi1-x) O 3(However, if 0 ≦ x ≦ 1
It 2) with respect to Pb in the dielectric crystal film of
Dielectric bonding characterized by containing 0 atomic% or less of K
Crystal film.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27126694A JP3531688B2 (en) | 1994-11-04 | 1994-11-04 | Dielectric crystal film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27126694A JP3531688B2 (en) | 1994-11-04 | 1994-11-04 | Dielectric crystal film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08133734A true JPH08133734A (en) | 1996-05-28 |
JP3531688B2 JP3531688B2 (en) | 2004-05-31 |
Family
ID=17497691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27126694A Expired - Lifetime JP3531688B2 (en) | 1994-11-04 | 1994-11-04 | Dielectric crystal film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3531688B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001015381A (en) * | 1999-06-28 | 2001-01-19 | Hokuriku Electric Ind Co Ltd | Surface-mounting type composite electronic component and manufacture thereof |
US6734036B2 (en) * | 2000-01-18 | 2004-05-11 | Agere Systems Inc. | Semiconductor device and method of fabrication |
-
1994
- 1994-11-04 JP JP27126694A patent/JP3531688B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001015381A (en) * | 1999-06-28 | 2001-01-19 | Hokuriku Electric Ind Co Ltd | Surface-mounting type composite electronic component and manufacture thereof |
US6734036B2 (en) * | 2000-01-18 | 2004-05-11 | Agere Systems Inc. | Semiconductor device and method of fabrication |
Also Published As
Publication number | Publication date |
---|---|
JP3531688B2 (en) | 2004-05-31 |
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