JP3531688B2 - Dielectric crystal film - Google Patents
Dielectric crystal filmInfo
- Publication number
- JP3531688B2 JP3531688B2 JP27126694A JP27126694A JP3531688B2 JP 3531688 B2 JP3531688 B2 JP 3531688B2 JP 27126694 A JP27126694 A JP 27126694A JP 27126694 A JP27126694 A JP 27126694A JP 3531688 B2 JP3531688 B2 JP 3531688B2
- Authority
- JP
- Japan
- Prior art keywords
- mmol
- substrate
- crystal film
- raw material
- 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.)
- Expired - Lifetime
Links
- 239000013078 crystal Substances 0.000 title claims description 41
- 239000000758 substrate Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical class ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 239000002253 acid Chemical class 0.000 claims 1
- 229940125810 compound 20 Drugs 0.000 claims 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 28
- 239000010936 titanium Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Insulating Materials (AREA)
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。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 Dielectric crystal films have a wide range of applications as electronic materials as described above. In particular, Pb (ZrTi) O 3 -based materials that are ferroelectrics have been studied in various ways, including their substitution and the effects of additives. However, ceramic materials that have been put to practical use so far are:
The Curie temperature is 200 to 400 ° C., and therefore, there has been a problem of performance deterioration due to temperature rise due to soldering. For example, it is used as a pyroelectric material (PbC
a) In a TiO 3 -based perovskite material, a 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, although attempts have been made to improve performance by thinning, conventional methods require heat treatment for crystallization after film formation or high temperature during film formation. I can't avoid it. For this reason, in the heat treatment step, a substrate having no mutual diffusion with the ferroelectric crystal film material should be selected, and in order to prevent cracks in the ferroelectric thin film material, the substrate should be made to have the same heat as the ferroelectric thin film material. There is a problem that it is necessary to select a substrate having an expansion coefficient.
【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。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a Pb (ZrTi) O 3 -based material which can be formed by a low-temperature process and has a high Curie temperature. With the goal.
【0004】[0004]
【課題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(ZrxTi1−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10原子%以上20原子%以下のK
を含有し、キュリー温度が500℃以上であることを特
徴とする誘電体結晶膜に関する。さらに、本発明は、P
b元素を含有する原料化合物50mmol/l〜500
mmol/l、Zr元素を含有する原料化合物20mm
ol/l〜500mmol/l、Ti元素を含有する原
料化合物0.002mmol/l〜50mmol/l、
およびKOH1mol/l〜8mol/lの混合水溶液
中に、Ti基板あるいはTiをコーティングした基板を
投入し、140〜190℃の温度で、水熱による表面処
理を行い、Pb(Zr xTi 1−x)O 3(ただし、0
<x<1である。)からなる結晶核を形成した後、Pb
元素を含有する原料化合物50mmol/l〜500m
mol/l、Zr元素を含有する原料化合物10mmo
l/l〜500mmol/l、Ti元素を含有する原料
化合物5mmol/l〜400mmol/l、およびK
OH2mol/l〜8mol/lの混合水溶液中に、前
記結晶核が形成された基板を投入して150〜200℃
水熱処理することを特徴とするPb(Zr xT
i 1−x)O 3(ただし、0<x<1である。)からな
る誘電体結晶膜の製造方法に関する。 The present invention SUMMARY OF], due hydrothermal synthesis formed on the substrate Pb (Zr x Ti 1-x ) O 3 ( however, 0 <x <1.) Dielectric crystal consisting of In the film, K not less than 10 atomic% and not more than 20 atomic% with respect to Pb
And a dielectric crystal film having a Curie temperature of 500 ° C. or higher . Furthermore, the present invention provides
Starting compound containing element b: 50 mmol / l to 500
mmol / l, raw material compound containing Zr element 20 mm
ol / l to 500 mmol / l, raw material containing Ti element
0.002 mmol / l to 50 mmol / l,
And KOH 1mol / l to 8mol / l mixed aqueous solution
Inside, place a Ti substrate or a substrate coated with Ti
At a temperature of 140 to 190 ° C.
And Pb (Zr x Ti 1-x ) O 3 (where 0
<X <1. ) After forming a crystal nucleus
Starting compound containing element 50 mmol / l to 500 m
mol / l, raw material compound containing Zr element 10mmo
l / l-500mmol / l, raw material containing Ti element
Compound 5 mmol / l to 400 mmol / l, and K
In a mixed aqueous solution of OH 2 mol / l to 8 mol / l,
The substrate on which the crystal nuclei are formed is put in, and 150 to 200 ° C.
Pb (Zr x T) characterized by hydrothermal treatment
i 1-x ) O 3 (where 0 <x <1).
A method for manufacturing a dielectric 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。[0005] Examples of the substrate used in the present invention include a metal plate, a metal plate having a surface oxidized, a resin substrate or an insulator substrate coated with 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, 1-100 μm is used as a substrate.
Using a metal substrate such as a titanium metal foil with a thickness of 50 m
When a ferroelectric crystal film having a thickness of not more than m, preferably not more than 10 μm is formed on a substrate by a hydrothermal synthesis method or the like, a ferroelectric crystal film having particularly high insulation resistance and low dielectric loss is obtained. Can be.
【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 for forming the ferroelectric crystal film layer of the present invention on a 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,
Raw material compounds containing Pb, Zr, and Ti constituent elements used when forming a ferroelectric crystal film by a hydrothermal method include chloride, oxychloride, nitrate, alkoxide, acetate, hydroxide, Oxides and the like are preferred. The ferroelectric crystal film is formed as follows.
【0008】まずPb(NO3)2水溶液50mmol
/l〜500mmol/l、ZrOCl2水溶液20m
mol/l〜500mmol/l、TiCl4水溶液
0.002mmol/l〜50mmol/lおよびKO
H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、6〜2
4時間水熱による表面処理を行い、Pb(ZrxTi
1−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, 50 mmol of Pb (NO 3 ) 2 aqueous solution
/ L to 500 mmol / l, ZrOCl 2 aqueous solution 20m
mol / l to 500 mmol / l, 0.002 mmol / l to 50 mmol / l of TiCl 4 aqueous solution and KO
In a mixed solution of 1 mol / l to 8 mol / l H aqueous solution,
The substrate is charged, and at a temperature of 140 to 190 ° C., 6 to 2
Surface treatment by hydrothermal treatment for 4 hours, and Pb (Zr x Ti
1-x ) A crystal nucleus composed of O 3 ( 0 <x <1 ) is formed. A ferroelectric crystal film with high orientation can be obtained by performing a hydrothermal reaction in the presence of a Ti-containing raw material compound during crystal nucleus formation and then performing 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 50mmol / l~500mmol / 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 put into a mixed solution of 8 mol / l and subjected to a hydrothermal treatment at 150 to 200 ° C. for 1 to 24 hours to perform rapid crystallization. Thus, a ferroelectric crystal film is formed on the substrate. The heating method in the hydrothermal treatment is based on an oil bath or an electric furnace. Thereafter, general cleaning is performed. For example, ultrasonic cleaning is performed in pure water, then ultrasonic cleaning is performed in an acetic acid aqueous solution, and then ultrasonic cleaning is performed in pure water.
Dry at 00 to 120 ° C for about 12 hours. The composition of the dielectric crystal film thus formed has a composition of 2 with respect to Pb.
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。[0010] The formation of crystal nuclei by the hydrothermal reaction is performed under the condition that the Reynolds number is 2000 or less, preferably 1000 or less, and then crystallized, whereby a ferroelectric thin film having more excellent orientation can be obtained. The crystal growth may be performed under a laminar flow or under a turbulent flow, but the film formation rate can be increased by appropriately 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 by the present invention is made into an element is not particularly limited, but an optimum electrode is selected in consideration of cost and mass productivity. For example, Ni by sputtering, Ni by electroless plating, baking Ag, etc. are selectively used. In addition, Al by vapor deposition, Pt or Au by sputtering, etc. are also used. When a resin is used for the substrate, it cannot be heated to a high temperature.
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。Embodiment 1
Pb (NOThree)TwoAqueous solution 16 mmol, ZrOClTwoAqueous solution
8 mmol, TiClFour0.08 mmol of aqueous solution and KOH water
In a mixed solution of 0.3 mol of solution (total volume of solution: 150 ml)
And fix the Ti substrate, and hydrothermal at 180 ° C for 12 hours
Pb (ZrTi) OThreeOf crystal nuclei
Was. Next, Pb (NOThree) TwoAqueous solution 16
mmol, ZrOClTwo8.32 mmol aqueous solution, TiClFourwater
Mixing 7.68 mmol of solution and 2.24 mol of aqueous KOH
Into a mixed solution (total amount of the solution: 640 ml),
Pb (Z
rTi) OThreeWas formed. After that, super sound in pure water
Ultrasonic washing in 1 mol / l acetic acid aqueous solution twice for 3 minutes x wave washing
Purification 3 times x 2 times, and further ultrasonic cleaning in pure water for 3 minutes
The drying was performed at 100 ° C. for 12 hours. This
FIG. 1 shows the X-ray diffraction pattern of the crystal film obtained as described above.
And in the film confirmed by ICP, EPMA, etc.
Was 10 atomic% with respect to Pb. This
Pb (ZrXTi1-X) OThree(However
And x is 0.52. ) The membrane is not polarized
Even after the heat treatment at 500 ° C
Also has a pyroelectric coefficient of 3.0 × 10-8[C / cmTwo・ K]
No, it was confirmed that the Curie temperature was 500 ° C or higher.
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 crystal nuclei were formed in the same manner as in Example 1, 16 mmol of a Pb (NO 3 ) 2 aqueous solution was used for crystal growth.
The mixture was put into a mixed solution (total amount of the solution: 640 ml) of a ZrOCl 2 aqueous solution (8.32 mmol), a TiCl 4 aqueous solution (7.68 mmol) and a KOH aqueous solution (2.56 mol).
A Pb (ZrTi) O 3 film was formed under hydrothermal conditions for a long time. Thereafter, the same cleaning as in Example 1 was performed. FIG. 2 shows the X-ray diffraction pattern of the crystal film thus obtained, and the K concentration in the film confirmed by ICP, EPMA or the like was 15 atomic% with respect to Pb. The Pb (Zr x Ti 1-x ) O 3 (x is 0.52) film produced in this way has a uniform polarization axis without any polarization treatment, and is subjected to a heat treatment at 500 ° C. , The pyroelectric coefficient was 2.5 × 10 −8 [C / cm 2 · K], and the Curie temperature was confirmed to be 500 ° C. or higher.
【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。As described above, Pb formed by hydrothermal synthesis and containing 20 atomic% or less of K with respect to Pb.
The (ZrTi) O 3 -based dielectric crystal film has a uniform polarization axis without any polarization treatment, and has a Curie temperature of 50.
Since the temperature is as high as 0 ° C. or more, there is no characteristic deterioration at the time of soldering or the like.
【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 shows Pb after a crystal growth reaction obtained according to the present invention.
FIG. 3 is a view showing an X-ray diffraction pattern of a (ZrTi) O 3 oriented crystal 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 shows Pb after a crystal growth reaction obtained according to the present invention.
FIG. 3 is a view showing an X-ray diffraction pattern of a (ZrTi) O 3 oriented crystal film.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平6−211523(JP,A) 特開 平5−139749(JP,A) 特開 平2−212316(JP,A) 特開 昭62−216917(JP,A) 特開 昭63−85015(JP,A) (58)調査した分野(Int.Cl.7,DB名) C01G 1/00 - 57/00 C30B 7/10 C30B 29/22 H01B 3/12 301 H01L 41/187 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-211523 (JP, A) JP-A-5-139749 (JP, A) JP-A-2-212316 (JP, A) JP-A 62-115 216917 (JP, A) JP-A-63-85015 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01G 1/00-57/00 C30B 7/10 C30B 29/22 H01B 3/12 301 H01L 41/187
Claims (4)
(ZrxTi1−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1
0原子%以上20原子%以下のKを含有し、キュリー温
度が500℃以上であることを特徴とする誘電体結晶
膜。1. Pb formed on a substrate by hydrothermal synthesis
(Zr x Ti 1-x) O 3 ( however, 0 <x <1.) In the dielectric crystal film consisting of, 1 for Pb
It contains 0 atomic% or more and 20 atomic% or less of K, and has a Curie temperature.
A dielectric crystal film having a temperature of 500 ° C. or higher .
ol/l〜500mmol/l、Zr元素を含有する原ol / l to 500 mmol / l, containing Zr element
料化合物20mmol/l〜500mmol/l、TiCompound 20 mmol / l to 500 mmol / l, Ti
元素を含有する原料化合物0.002mmol/l〜5Starting compound containing element 0.002 mmol / l to 5
0mmol/l、およびKOH1mol/l〜8mol0 mmol / l, and KOH 1 mol / l to 8 mol
/lの混合水溶液中に、Ti基板あるいはTiをコーテ/ L of a mixed aqueous solution of Ti substrate or Ti
ィングした基板を投入し、140〜190℃の温度で、Into the substrate, and at a temperature of 140 to 190 ° C,
水熱による表面処理を行い、Pb(ZrAfter performing surface treatment with hydrothermal heat, Pb (Zr xTi x Ti 1−x) 1-x )
OO 3(ただし、0<x<1である。)からなる結晶核を 3 (where 0 <x <1)
形成した後、After forming Pb元素を含有する原料化合物50mmol/l〜50Starting compound containing Pb element 50 mmol / l to 50
0mmol/l、Zr元素を含有する原料化合物10m0 mmol / l, raw material compound containing Zr element 10 m
mol/l〜500mmol/l、Ti元素を含有するmol / l to 500 mmol / l, containing Ti element
原料化合物5mmol/l〜400mmol/l、およStarting material compound 5 mmol / l to 400 mmol / l, and
びKOH2mol/l〜8mol/lの混合水溶液中And KOH 2mol / l to 8mol / l mixed aqueous solution
に、前記結晶核が形成された基板を投入して150〜2The substrate on which the crystal nuclei are formed is put into
00℃水熱処理することを特徴とするPb(ZrPb (Zr xTi x Ti
1−x)O 1-x ) O 3(ただし、0<x<1である。)からなる 3 (where 0 <x <1)
誘電体結晶膜の製造方法。A method for manufacturing a dielectric crystal film.
r元素を含有する原料化合物、およびTi元素を含有すa raw material compound containing an r element, and a
る原料化合物が、それぞれ、塩化物、オキシ塩化物、硝Starting compounds are chloride, oxychloride,
酸塩、アルコキシド、酢酸塩、水酸化物、または酸化物Acid salts, alkoxides, acetates, hydroxides or oxides
であることを特徴とする請求項2記載の強誘電体結晶膜3. The ferroelectric crystal film according to claim 2, wherein
の製造方法。Manufacturing method.
b(NO3)2であり、前記Zr元素を含有する原料化b (NO3) 2, a raw material containing the Zr element
合物がZrOClThe compound is ZrOCl 2であり、前記Ti元素を含有する原 2 and an element containing the Ti element.
料化合物がTiClThe charge compound is TiCl 4であることを特徴とする請求項2 4. The method according to claim 2, wherein
記載の強誘電体結晶膜の製造方法。A method for producing a ferroelectric crystal film according to the above.
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JP27126694A JP3531688B2 (en) | 1994-11-04 | 1994-11-04 | Dielectric crystal film |
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JP3531688B2 true JP3531688B2 (en) | 2004-05-31 |
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JP2001015381A (en) * | 1999-06-28 | 2001-01-19 | Hokuriku Electric Ind Co Ltd | Surface-mounting type composite electronic component and manufacture thereof |
US6437425B1 (en) * | 2000-01-18 | 2002-08-20 | Agere Systems Guardian Corp | Semiconductor devices which utilize low K dielectrics |
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1994
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